TY - JOUR A1 - Marco Figuera, Ramiro A1 - Riedel, Christian A1 - Rossi, Angelo Pio A1 - Unnithan, Vikram T1 - Depth to diameter analysis on small simple craters at the lunar south pole - possible implications for ice harboring JF - Remote sensing N2 - In this paper, we present a study comparing the depth to diameter (d/D) ratio of small simple craters (200-1000 m) of an area between -88.5 degrees to -90 degrees latitude at the lunar south pole containing Permanent Shadowed Regions (PSRs) versus craters without PSRs. As PSRs can reach temperatures of 110 K and are capable of harboring volatiles, especially water ice, we analyzed the relationship of depth versus diameter ratios and its possible implications for harboring water ice. Variations in the d/D ratios can also be caused by other processes such as degradation, isostatic adjustment, or differences in surface properties. The conducted d/D ratio analysis suggests that a differentiation between craters containing PSRs versus craters without PSRs occurs. Thus, a possible direct relation between d/D ratio, PSRs, and water ice harboring might exist. Our results suggest that differences in the target's surface properties may explain the obtained results. The resulting d/D ratios of craters with PSRs can help to select target areas for future In-Situ Resource Utilization (ISRU) missions. KW - craters KW - lunar exploration KW - ice harboring Y1 - 2022 U6 - https://doi.org/10.3390/rs14030450 SN - 2072-4292 VL - 14 IS - 3 PB - MDPI CY - Basel ER - TY - JOUR A1 - Raman Venkatesan, Thulasinath A1 - Smykalla, David A1 - Ploss, Bernd A1 - Wübbenhorst, Michael A1 - Gerhard, Reimund T1 - Non-linear dielectric spectroscopy for detecting and evaluating structure-property relations in a P(VDF-TrFE-CFE) relaxor-ferroelectric terpolymer JF - Applied physics : A, Materials science & processing N2 - Non-linear dielectric spectroscopy (NLDS) is employed as an effective tool to study relaxation processes and phase transitions of a poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) relaxor-ferroelectric (R-F) terpolymer in detail. Measurements of the non-linear dielectric permittivity epsilon 2 ' reveal peaks at 30 and 80 degrees C that cannot be identified in conventional dielectric spectroscopy. By combining the results from NLDS experiments with those from other techniques such as thermally stimulated depolarization and dielectric-hysteresis studies, it is possible to explain the processes behind the additional peaks. The former peak, which is associated with the mid-temperature transition, is found in all other vinylidene fluoride-based polymers and may help to understand the non-zero epsilon 2 ' values that are detected on the paraelectric phase of the terpolymer. The latter peak can also be observed during cooling of P(VDF-TrFE) copolymer samples at 100 degrees C and is due to conduction and space-charge polarization as a result of the accumulation of real charges at the electrode-sample interface. KW - Non-linear dielectric spectroscopy KW - P(VDF-TrFE-CFE) KW - Relaxor-ferroelectric polymer KW - Dielectric hysteresis KW - Curie-transition KW - Mid-temperature transition Y1 - 2021 U6 - https://doi.org/10.1007/s00339-021-04876-0 SN - 0947-8396 SN - 1432-0630 VL - 127 IS - 10 PB - Springer CY - Berlin ; Heidelberg ; New York ER - TY - JOUR A1 - Gerhard, Reimund A1 - Kacprzyk, Ryszard T1 - Paul Böning - early electret researcher in Shanghai and Wroclaw (1922-1945) JF - IEEE transactions on dielectrics and electrical insulation N2 - The scientific career and the research activities of Paul Boening, especially during his tenures at Tongji University in Shanghai (Woosung Campus, 1922-1936) and the Technical University of Wroclaw (TH Breslau, 1936-1945), are briefly reviewed. In particular, Boening's pioneering investigations in the area of electrets and space charge in dielectrics are emphasized. We attempt to shed some light on the significant achievements of a virtually unknown contributor to the early history of electrets and of space-charge research and high-voltage engineering, during the 1920s and 1930s. It should be noted that dielectrics research was a truly international endeavor already at that time. KW - dielectrics KW - electrets KW - electrostatic KW - experiments KW - (high-)voltage measurements KW - space charge Y1 - 2022 U6 - https://doi.org/10.1109/TDEI.2022.3168372 SN - 1070-9878 SN - 1558-4135 VL - 29 IS - 3 SP - 853 EP - 858 PB - Institute of Electrical and Electronics Engineers CY - New York, NY ER - TY - JOUR A1 - Spelzhausen, Simon A1 - Ionian, Mario-Rafael A1 - Gerhard, Reimund A1 - Plath, Ronald T1 - Time-resolved measurement of space-charge evolution in dielectric films or slabs by means of repeatable laser-induced pressure pulses JF - Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques N2 - A new variant of the Laser-Induced Pressure-Pulse (LIPP) method for repeatable, time-resolved space-charge profile measurements is proposed and demonstrated. Automated deposition of a fresh laser-target film before each illumination leads to good repeatability of the LIPP and thus allows for the detection of time-resolved changes in the space-charge distribution over many hours. We describe and discuss the experimental setup and its features, compare the repeatability of the LIPP measurements on the same sample without and with re-preparation of the test cell, and present the time-resolved evolution of the space-charge profile in a two-layer arrangement of a silicone-grease and a silicone-elastomer film as an example. Finally, the temperature dependence of the space-charge evolution during polarization under high voltage and during depolarization in short circuit is shown. Possible uses and future developments of the new LIPP approach are also discussed. Y1 - 2020 U6 - https://doi.org/10.1063/1.5142443 SN - 0034-6748 SN - 1089-7623 VL - 91 IS - 5 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Frübing, Peter A1 - Kremmer, Alexander A1 - Gerhard, Reimund A1 - Spanoudaki, Anna A1 - Pissis, Polycarpos T1 - Relaxation processes at the glass transition in polyamide 11: From rigidity to viscoelasticity JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - Relaxation processes associated with the glass transition in nonferroelectric and ferroelectric polyamide (PA) 11 are investigated by means of differential scanning calorimetry, dynamic mechanical analysis, and dielectric relaxation spectroscopy (DRS) in order to obtain information about the molecular mobility within the amorphous phase. In particular, the effects of melt quenching, cold drawing, and annealing just below the melting region are studied with respect to potential possibilities and limitations for improving the piezoelectric and pyroelectric properties of PA 11. A relaxation map is obtained from DRS that shows especially the crossover region where the cooperative alpha relaxation and the local beta relaxation merge into a single high-temperature process. No fundamental difference between quenched, cold-drawn, and annealed films is found, though in the cold-drawn (ferroelectric) film the alpha relaxation is suppressed and slowed down, but it is at least partly recovered by subsequent annealing. It is concluded that there exists an amorphous phase in all structures, even in the cold-drawn film. The amorphous phase can be more rigid or more viscoelastic depending on preparation. Cold drawing not only leads to crystallization in a ferroelectric form but also to higher rigidity of the remaining amorphous phase. Annealing just below the melting region after cold drawing causes a stronger phase separation between the crystalline phase and a more viscoelastic amorphous phase. Y1 - 2006 U6 - https://doi.org/10.1063/1.2360266 SN - 0021-9606 VL - 125 IS - 12 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Flores Suárez, Rosaura A1 - Mellinger, Axel A1 - Wegener, Michael A1 - Wirges, Werner A1 - Gerhard, Reimund A1 - Singh, Rajeev T1 - Thermal-pulse tomography of polarization distributions in a cylindrical geometry JF - IEEE transactions on dielectrics and electrical insulation N2 - Fast, three-dimensional polarization mapping in piezoelectric sensor cables was performed by means of the novel thermal-pulse tomography (TPT) technique with a lateral resolution of 200 mum. The active piezoelectric cable material (a copolymer of polyvinylidene fluoride with trifluoroethylene) was electrically poled with a point-to-cable corona discharge. A focused laser was employed to heat the opaque outer electrode, and the short-circuit current generated by the thermal pulse was used to obtain 3D polarization maps via the scale transformation method. The article describes the TPT technique as a fast non-destructive option for studying cylindrical geometries. Y1 - 2006 U6 - https://doi.org/10.1109/TDEI.2006.258210 SN - 1070-9878 VL - 13 IS - 5 SP - 1030 EP - 1035 PB - IEEE CY - Piscataway ER - TY - JOUR A1 - Raman Venkatesan, Thulasinath A1 - Gulyakova, Anna A. A1 - Frübing, Peter A1 - Gerhard, Reimund T1 - Electrical polarization phenomena, dielectric relaxations and structural transitions in a relaxor-ferroelectric terpolymer investigated with electrical probing techniques JF - Materials research express N2 - Dielectric Relaxation Spectroscopy (DRS) and Thermally Stimulated Depolarization Current (TSDC) measurements were employed to study dielectric-relaxation processes, structural transitions and electric-polarization phenomena in poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer films. Results from DRS confirm the existence of two separate dispersion regions related to a para-to-ferroelectric phase transition and to the glass transition. The dipolar TSDC peak correlates with the loss peak of the ? relaxation that represents the glass transition. The electric polarization calculated from the dipolar TSDC peak (glass transition) shows a non-linear electric-field dependence and saturates at high electric poling fields. As the observed behaviour is essentially the same as that of the electric polarization obtained from direct polarization-versus-electric-field hysteresis measurements, TSDC experiments are also suitable for studying the polarization in relaxor-ferroelectric polymers. A saturation polarization of 44 mC m(?2) was found for an electric field of 190 MV m(?1). KW - P(VDF-TrFE-CFE) terpolymer KW - relaxor-ferroelectric polymers KW - dielectric relaxation spectroscopy KW - thermally stimulated depolarization current KW - electrical polarization hysteresis Y1 - 2019 U6 - https://doi.org/10.1088/2053-1591/ab5352 SN - 2053-1591 VL - 6 IS - 12 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Raman Venkatesan, Thulasinath A1 - Smykalla, David A1 - Ploss, Bernd A1 - Wübbenhorst, Michael A1 - Gerhard, Reimund T1 - Tuning the relaxor-ferroelectric properties of Poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) Terpolymer films by means of thermally induced micro- and nanostructures JF - Macromolecules : a publication of the American Chemical Society N2 - The effects of thermal processing on the micro- and nanostructural features and thus also on the relaxor-ferroelectric properties of a P(VDF-TrFE-CFE) terpolymer were investigated in detail by means of dielectric experiments, such as dielectric relaxation spectroscopy (DRS), dielectric hysteresis loops, and thermally stimulated depolarization currents (TSDCs). The results were correlated with those obtained from differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and Fourier-transform infrared spectroscopy (FTIR). The results from DRS and DSC show that annealing reduces the Curie transition temperature of the terpolymer, whereas the results from WAXD scans and FTIR spectra help to understand the shift in the Curie transition temperatures as a result of reducing the ferroelectric phase fraction, which by default exists even in terpolymers with relatively high CFE contents. In addition, the TSDC traces reveal that annealing has a similar effect on the midtemperature transition by altering the fraction of constrained amorphous phase at the interphase between the crystalline and the amorphous regions. Changes in the transition temperatures are in turn related to the behavior of the hysteresis curves on differently heat-treated samples. During heating, evolution of the hysteresis curves from ferroelectric to relaxor-ferroelectric, first exhibiting single hysteresis loops and then double hysteresis loops near the Curie transition of the sample, is observed. When comparing the dielectric-hysteresis loops obtained at various temperatures, we find that annealed terpolymer films show higher electric-displacement values and lower coercive fields than the nonannealed sample, irrespective of the measurement temperature, and also exhibit ideal relaxor- ferroelectric behavior at ambient temperatures, which makes them excellent candidates for applications at or near room temperature. By tailoring the annealing conditions, it has been shown that the application temperature could be increased by fine tuning the induced micro- and nanostructures. KW - Annealing (metallurgy) KW - Hysteresis KW - Insulators KW - Phase transitions KW - Polarization Y1 - 2022 U6 - https://doi.org/10.1021/acs.macromol.2c00302 SN - 0024-9297 SN - 1520-5835 VL - 55 IS - 13 SP - 5621 EP - 5635 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Raman Venkatesan, Thulasinath A1 - Gulyakova, Anna A. A1 - Frübing, Peter A1 - Gerhard, Reimund T1 - Relaxation processes and structural transitions in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) relaxor-ferroelectric terpolymers as seen in dielectric spectroscopy JF - IEEE transactions on dielectrics and electrical insulation N2 - Dielectric relaxation processes and structural transitions in Poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer films with two different monomer compositions were investigated in comparison with Poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) copolymer films as reference material. Differential Scanning Calorimetry was employed to assess annealing effects on phase transitions and crystalline structure, while relaxation processes were investigated by means of Dielectric Relaxation Spectroscopy, the results of which indicate the existence of two separate dispersion regions, denoted as processes A and B, respectively. Process A appears at a certain temperature independent of frequency, but is strongly influenced by the crystallisation temperature and the CFE content, while peak B shows typical features of a relaxation process and is less influenced by crystallisation temperature and CFE content. Furthermore, peak B is related to the glass transition which is more pronounced in the terpolymer than in P(VDF-TrFE). A closer analysis indicates that the addition of CFE and thermal annealing gradually shift the ferro-to-paraelectric transition in P(VDF-TrFE) to lower temperatures, while the phase transition is transformed more and more into a relaxation. KW - P(VDF-TrFE-CFE) terpolymer KW - relaxor-ferroelectric polymer KW - dielectric relaxation spectroscopy KW - Curie transition KW - differential scanning calorimetry Y1 - 2018 U6 - https://doi.org/10.1109/TDEI.2018.007440 SN - 1070-9878 SN - 1558-4135 VL - 25 IS - 6 SP - 2229 EP - 2235 PB - Institut of Electrical and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Qiu, Xunlin A1 - Groth, Frederick A1 - Wirges, Werner A1 - Gerhard, Reimund T1 - Cellular polypropylene foam films as DC voltage insulation and as piezoelectrets BT - a comparison JF - IEEE transactions on dielectrics and electrical insulation N2 - Polymer foams are in industrial use for several decades. More recently, non-polar polymer foams were found to be piezoelectric (so-called piezoelectrets) after internal electrical charging of the cavities. So far, few studies have been carried out on the electrical-insulation properties of polymer foams. Here, we compare the piezoelectric and the DC-voltage electrical-insulation properties of cellular polypropylene (PP) foams. Their cavity microstructure can be adjusted via inflation in high-pressure nitrogen gas in combination with a subsequent thermal treatment. While inflation is effective for improving the piezoelectricity, it is detrimental for the electrical-insulation properties. The original cellular PP foam shows a breakdown strength of approximately 230 MV/m, within the same range as that of solid PP. The breakdown strength decreases with increasing degree of inflation, and the dependence on the foam thickness follows an inverse power law with an exponent of 1.2. Nevertheless, up to a thickness of 140 mu m (3.5 times the original thickness), the breakdown strength of cellular-foam PP films is at least 7 times that of an air gap with the same thickness. In addition, the influence of high temperatures and high humidities on the piezoelectricity and the breakdown strength of cellular PP was studied. It was found that the piezoelectric d(33) coefficient decays rapidly already at 70 degrees C, while the breakdown strength slightly increases during storage at 70 or 90 degrees C. Under a relative humidity of 95%, the breakdown strength increases with storage time, while the piezoelectric d(33) coefficient slightly decreases. KW - Cellular polypropylene (PP) KW - polymer-foam films KW - ferro- and piezoelectrets KW - charge storage KW - electrical breakdown KW - dielectric barrier discharges Y1 - 2018 U6 - https://doi.org/10.1109/TDEI.2018.007192 SN - 1070-9878 SN - 1558-4135 VL - 25 IS - 3 SP - 829 EP - 834 PB - Institut of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Rychkov, Dmitry A1 - Gerhard, Reimund A1 - Kuznetsov, Alexey A1 - Rychkov, Andrey T1 - Influence of charge density on the trap energy spectrum in fluoroethylenepropylene copolymer films with chemically modified surfaces JF - IEEE transactions on dielectrics and electrical insulation N2 - Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) films were treated with titanium-tetrachloride vapor by means of molecular-layer deposition. The treatment leads to considerable improvements of the electret-charge stability on positively charged films. A slight improvement is also observed for negatively charged films. In line with our previous findings, we attribute the improvement in electret properties to the formation of deeper traps on the chemically modified polymer surfaces. Here, we investigate the influence of the charge density on electret stability of FEP films with modified surfaces. Trap-energy spectra obtained from thermally-stimulated-discharge measurements indicate that the charge stability on modified FEP films depends on how the surface traps are populated and on the availability of additional deeper traps. KW - Electrets KW - chemical modification KW - surface treatment KW - space-charge stability KW - charge-carrier transport KW - polytetrafluoroethylene (PTFE) KW - fluoroethylenepropylene (FEP) copolymer Y1 - 2018 U6 - https://doi.org/10.1109/TDEI.2018.007437 SN - 1070-9878 SN - 1558-4135 VL - 25 IS - 3 SP - 840 EP - 844 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Fang, Peng A1 - Ma, Xingchen A1 - Li, Xiangxin A1 - Qiu, Xunlin A1 - Gerhard, Reimund A1 - Zhang, Xiaoqing A1 - Li, Guanglin T1 - Fabrication, Structure Characterization, and Performance Testing of Piezoelectret-Film Sensors for Recording Body Motion JF - IEEE Sensors Journal N2 - During muscle contractions, radial-force distributions are generated on muscle surfaces due to muscle-volume changes, from which the corresponding body motions can be recorded by means of so-called force myography (FMG). Piezo- or ferroelectrets are flexible piezoelectric materials with attractive materials and sensing properties. In addition to several other applications, they are suitable for detecting force variations by means of wearable devices. In this paper, we prepared piezoelectrets from cellular polypropylene films by optimizing the fabrication procedures, and developed an FMG-recording system based on piezoelectret sensors. Different hand and wrist movements were successfully detected on able-bodied subjects with the FMG system. The FMG patterns were evaluated and identified by means of linear discriminant analysis and artificial neural network algorithms, and average motion-classification accuracies of 96.1% and 94.8%, respectively, were obtained. This paper demonstrates the feasibility of using piezoelectret-film sensors for FMG and may thus lead to alternative methods for detecting body motion and to related applications, e.g., in biomedical engineering or structural-health monitoring. KW - Forcemyography KW - motion registration KW - piezoelectret KW - film sensor KW - wearable Y1 - 2017 U6 - https://doi.org/10.1109/JSEN.2017.2766663 SN - 1530-437X SN - 1558-1748 VL - 18 IS - 1 SP - 401 EP - 412 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Gidion, Gunnar A1 - Gerhard, Reimund T1 - The Bow on a String BT - Bow Vibrations Detected with Ferroelectret Sensors JF - Acta Acustica united with Acustica N2 - The interaction between a bowed string instrument and its player is conveyed by the bow, the vibrational properties of which can be measured either separately on the bow or during the bowing procedure. Here, two piezoelectric film sensors, made of a ferroelectret material, are installed on a violin bow, one sensor at the tip and one at the frog. With these sensors, a violin is played under normal conditions, and the signals are analysed. The features in the resulting spectrograms are identified as string harmonics and longitudinal bow-hair resonances. The bow-hair sections on both sides of the bow-string contact exhibit separate resonances which are observed as absorption dips in the spectra. Owing to the sensor positions at the bow-hair terminations, it can be inferred that the two bow-hair sections act as mutual vibration absorbers. From a regression of the observed resonances, the longitudinal bow-hair velocity can be obtained. With additional film sensors under the violin bridge, body vibrations were also detected providing further details of the coupling mechanisms. Y1 - 2018 U6 - https://doi.org/10.3813/AAA.919174 SN - 1610-1928 SN - 1861-9959 VL - 104 IS - 2 SP - 315 EP - 322 PB - Hirzel Verlag CY - Stuttgart ER - TY - JOUR A1 - Wang, Jingwen A1 - Rychkov, Dmitry A1 - Gerhard, Reimund T1 - Space-charge electret properties of polypropylene films with transcrystalline or spherulitic structures BT - a comparison of functionalities at interfaces JF - Journal of applied physics : AIP's archival journal for significant new results in applied physics / publ. by the American Institute of Physics N2 - Spherulite-related space-charge electret properties of polypropylene (PP) have been widely discussed in the past decades. In the present paper, a less-common crystalline structure in PP-transcrystalline PP-is studied regarding its electret behavior in comparison with the typical spherulitic morphology. Polarized light microscopy and differential scanning calorimetry were employed to characterize the crystallite types and crystallinities of transcrystalline and spherulitic PP. Their electret functionality is investigated by means of thermally stimulated discharge experiments, where the cross-over phenomenon is observed on transcrystalline PP films, whereas surface-potential saturation and undercharging on the surface occur on the spherulitic samples. Besides, an asymmetrical behavior of positive and negative surface-charge stabilities is found on PP with spherulites, the negatively charged spherulitic surfaces show a better charge stability. It is shown that PP electrets are very sensitive to changes in the microscopic crystalline structures and their interfaces as well as in the molecular conformations controlled through adjustments of the respective processing steps. In addition, surface and bulk nanocomposites of PP or low-density polyethylene with inorganic particles are included in the comparison. In view of recent developments in the areas of PP-based electret-fiber filters and cellular-foam ferroelectrets, the observed changes in the charge-storage properties may have particular relevance, as the required film, fiber, or foam processing might significantly modify crystalline morphologies and nano-scale interfaces in PP electrets. Limitations in the charge-storage capabilities of interface structures may also be of interest in the context of high-voltage electrical-insulation materials where reduced space-charge accumulation and slightly increased charge transport can be advantageous. Y1 - 2021 U6 - https://doi.org/10.1063/5.0039867 SN - 0021-8979 SN - 1089-7550 VL - 129 IS - 6 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Qiu, Xunlin A1 - Benjamin, Aravindan Joseph A1 - Raman Venkatesan, Thulasinath A1 - Schmidt, Georg C. A1 - Soler, Ricardo Alonso Quintana A1 - Panicker, Pramul Muraleedhara A1 - Gerhard, Reimund A1 - Hübler, Arved Carl T1 - Dielectric and electroacoustic assessment of screen-printed piezoelectric polymer layers as flexible transducers BT - influence of the electrode material JF - IEEE transactions on dielectrics and electrical insulation N2 - Here, piezoelectric transducers consisting of a P(VDF-TrFE) layer with either silver or PEDOT:PSS screen-printed electrodes are studied. The influence of electrodes on the dielectric and electroacoustic properties are studied in dielectric-spectroscopy and ferroelectric-hysteresis measurements. Only when both the bottom and the top electrodes are made of silver, the typical dielectric relaxation of the P(VDF-TrFE) layer is clearly observed. When one or two of the electrodes are of PEDOT:PSS, a Debye-like relaxation is present. Compared with silver electrodes, PEDOT:PSS electrodes allow for moderate self-healing. Consequently, samples with bottom and top PEDOT:PSS electrodes can be poled to saturation, while samples with silver electrodes can hardly be poled to saturation due to destructive electric breakdown. Acoustic transducer measurements show that silver electrodes facilitate higher and broader frequency operation, while PEDOT:PSS electrodes bring slightly lower total harmonic distortion. Overall, the acoustic performance shows no significant deviations between differently electroded samples so that silver electrodes do not offer any advantages for the transducers studied here due to their much higher tendency for destructive electric breakdown. KW - poly(vinylidenefluoride-trifluoroethylene) P(VDF-TrFE) KW - dielectric KW - spectroscopy KW - ferroelectricity and piezoelectricity in polymers KW - screen KW - printing KW - printed electroacoustic thin-film transducers Y1 - 2020 U6 - https://doi.org/10.1109/TDEI.2020.008864 SN - 1070-9878 SN - 1558-4135 SN - 0018-9367 VL - 27 IS - 5 SP - 1683 EP - 1690 PB - Institute of Electrical and Electronics Engineers CY - New York, NY ER - TY - JOUR A1 - Wang, Jingwen A1 - Rychkov, Dmitry A1 - Nguyen, Quyet Doan A1 - Gerhard, Reimund T1 - The influence of orthophosphoric-acid surface modification on charge-storage enhancement in polypropylene electrets JF - Journal of applied physics N2 - Bipolar electrets from polypropylene (PP) are essential, e.g., in electret air filters and in cellular-foam ferroelectrets. Therefore, the mechanism of surface-charge stability enhancement on PP electrets via orthophosphoric-acid surface treatment is investigated in detail. It is shown that the significant charge-stability enhancement can be mainly attributed to deeper surface traps originating from deposited chemicals and topographic features on the modified surfaces. Thermally stimulated discharge of chemically treated and non-treated PP films with different surface-charge densities is used to test the limits of the newly formed deep traps in terms of the capacity for hosting surface charges. When the initial surface-charge density is very high, more charges are forced into shallower original traps on the surface or in the bulk of the treated PP samples, reducing the effect of the deeper surface traps brought by the surface modification. The well-known crossover phenomenon (of the surface-charge decay curves) has been observed between modified PP electrets charged to +/- 2kV and to +/- 3kV. Acoustically probed charge distributions in the thickness direction of PP electrets at different stages of thermal discharging indicate that the deep surface trapping sites may have preference for negative charges, resulting in the observed asymmetric charge stability of the modified PP films. Y1 - 2020 U6 - https://doi.org/10.1063/5.0013805 SN - 0021-8979 SN - 1089-7550 VL - 128 IS - 3 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Wang, Jingwen A1 - Rychkov, Dmitry A1 - Nguyen, Quyet Doan A1 - Gerhard, Reimund T1 - Unexpected bipolar space-charge polarization across transcrystalline interfaces in polypropylene electret films JF - Journal of applied physics N2 - A double-layer transcrystalline polypropylene (PP) film with a flat central interface layer between its two transcrystalline layers is obtained by recrystallization from the melt between two polytetrafluoroethylene (PTFE) surfaces on both sides of the PP film. Its electret properties are studied and compared with those of a single-layer transcrystalline PP film re-crystallized in contact with only one PTFE surface. Within experimental uncertainty, the two types of transcrystalline films exhibit the same thermal properties and crystallinities. After thermal poling, however, two hetero-charge layers of opposite polarity are found on the internal interfaces of the double-layer transcrystalline films and may together be considered as micrometer-sized dipoles. The unexpected phenomenon does not occur in single-layer transcrystalline samples without a central interface layer, suggesting that the interfaces between the transcrystalline layers and the micrometer-thick central interface layer may be the origin of deeper traps rather than the crystalline structures in the transcrystallites or the spherulites. The origin of the interfacial charges was also studied by means of an injection-blocking charging method, which revealed that intrinsic charge carriers introduced during recrystallization are most likely responsible for the interfacial charges. It is fascinating that a material as familiar as PP can exhibit such intriguing properties with a special bipolar space-charge polarization across the central interface layer after quasi-epitaxial surface moulding into a double-layer transcrystalline form. In addition to applications in electret (micro-)devices for electro-mechanical transduction, the highly ordered structures may also be employed as a new paradigm for studying charge storage and transport in polymer electrets and in dielectrics for DC electrical insulation. Y1 - 2020 U6 - https://doi.org/10.1063/5.0022071 SN - 0021-8979 SN - 1089-7550 VL - 128 IS - 13 PB - American Institute of Physics, AIP CY - Melville, NY ER - TY - JOUR A1 - Li, Changsheng A1 - Chen, Gangjin A1 - Qiu, Xunlin A1 - Gao, Meng A1 - Gerhard, Reimund T1 - Modified polytetrafluoroethylene BT - towards easy-to-process space-charge electret materials JF - Applied physics express : APEX N2 - Three poly(tetrafluoroethylene-hexafluoropropylene-vinylidenefluoride) (TFE-HFP-VDF or THV) terpolymers (Dyneon (R)) with different monomer ratios are investigated to demonstrate the concept of "modified" PTFE for space-charge electrets. HFP and VDF monomers distort the highly ordered PTFE molecules, which effectively enhances processability and adversely affects space-charge storage. Particularly, VDF component renders the material polar and probably also more conductive, partially undermining the space-charge-storage capabilities of PTFE. Nevertheless, the terpolymer THV815 with a TFE/HFP/VDF wt% ratio of 76.1/10.9/13 combines easy processability and relatively good space-charge stability. Our results shed light on novel concepts for space-charge electret materials with enhanced processing properties and reasonable charge-storage capabilities. Y1 - 2019 U6 - https://doi.org/10.7567/1882-0786/ab5b23 SN - 1882-0778 SN - 1882-0786 VL - 13 IS - 1 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Raman Venkatesan, Thulasinath A1 - Wübbenhorst, Michael A1 - Gerhard, Reimund T1 - Structure-property relationships in three-phase relaxor-ferroelectric terpolymers JF - Ferroelectrics N2 - Poly(vinylidenefluoride-trifluoroethylene)-based (P(VDF-TrFE)-based) terpolymers represent a new class of electroactive polymer materials that are relaxor-ferroelectric (RF) polymers and that offer unique and attractive property combinations in comparison with conventional ferroelectric polymers. The RF state is achieved by introducing a fluorine-containing termonomer as a "defect" into the ferroelectric P(VDF-TrFE) copolymer, which reduces the interaction between the VDF/TrFE dipoles. The resulting terpolymer exhibits a low Curie transition temperature and small remanent and coercive fields yielding a slim hysteresis loop that is typical for RF materials. Though the macroscopic behavior is similar to RF ceramics, the mechanisms of relaxor ferroelectricity in semi-crystalline polymers are different and not fully understood yet. Structure-property relationships play an important role in RF terpolymers, as they govern the final RF properties. Hence, a review of important characteristics, previous studies and relevant developments of P(VDF-TrFE)-based terfluoropolymers with either chlorofluoroethylene (CFE) or chlorotrifluoroethylene (CTFE) as the termonomer is deemed useful. The role of the termonomer and of its composition, as well as the effects of the processing conditions on the semi-crystalline structure which in turn affects the final RF properties are discussed in detail. In addition, the presence of noteworthy transition(s) in the mid-temperature range and the influence of preparation conditions on those transitions are reviewed. A better understanding of the fundamental aspects affecting the semi-crystalline structures will help to elucidate the nature of RF activity in VDF-based terpolymers and also help to further improve their applications-relevant electroactive properties. KW - Relaxor-ferroelectric (RF) fluoropolymers KW - structure-property KW - relationships KW - Curie transition KW - dielectric hysteresis KW - thermal KW - processing KW - mid-temperature transition(s) Y1 - 2022 U6 - https://doi.org/10.1080/00150193.2021.2014260 SN - 0015-0193 SN - 1563-5112 VL - 586 IS - 1 SP - 60 EP - 81 PB - Routledge, Taylor & Francis Group CY - Abingdon ER - TY - JOUR A1 - Assagra, Yuri A.O. A1 - Altafim, Ruy Alberto Pisani A1 - do Carmo, Joao P. A1 - Altafim, Ruy A.C. A1 - Rychkov, Dmitry A1 - Wirges, Werner A1 - Gerhard, Reimund T1 - A new route to piezo-polymer transducers: 3D printing of polypropylene ferroelectrets JF - IEEE transactions on dielectrics and electrical insulation N2 - Here, a promising approach for producing piezo-polymer transducers in a one-step process is presented. Using 3D-printing technology and polypropylene (PP) filaments, we are able to print a two-layered film structure with regular cavities of precisely controlled size and shape. It is found that the 3D-printed samples exhibit piezoelectric coefficients up to 200 pC/N, similar to those of other PP ferroelectrets, and their temporal and thermal behavior is in good agreement with those known of PP ferroelectrets. The piezoelectric response strongly decreases for applied pressures above 20 kPa, as the pressure in the air-filled cavities strongly influences the overall elastic modulus of ferroelectrets. KW - 3D printing KW - polymer ferroelectrets KW - sensors and actuators KW - piezoelectrets KW - electret polymers KW - soft electro-active materials KW - functional materials KW - soft matter Y1 - 2020 U6 - https://doi.org/10.1109/TDEI.2020.008461 SN - 1070-9878 SN - 1558-4135 VL - 27 IS - 5 SP - 1668 EP - 1674 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Rüdiger, Günther A1 - Schultz, Manfred A1 - Hollerbach, Rainer T1 - Destabilization of super-rotating Taylor-Couette flows by current-free helical magnetic fields JF - Journal of plasma physics N2 - In an earlier paper we showed that the combination of azimuthal magnetic fields and super-rotation in Taylor-Couette flows of conducting fluids can be unstable against non-axisymmetric perturbations if the magnetic Prandtl number of the fluid is Pm not equal 1. Here we demonstrate that the addition of a weak axial field component allows axisymmetric perturbation patterns for Pm of order unity depending on the boundary conditions. The axisymmetric modes only occur for magnetic Mach numbers (of the azimuthal field) of order unity, while higher values are necessary for the non-axisymmetric modes. The typical growth time of the instability and the characteristic time scale of the axial migration of the axisymmetric mode are long compared with the rotation period, but short compared with the magnetic diffusion time. The modes travel in the positive or negative z direction along the rotation axis depending on the sign of B phi Bz. We also demonstrate that the azimuthal components of flow and field perturbations travel in phase if vertical bar B phi vertical bar >> vertical bar B-z vertical bar, independent of the form of the rotation law. Within a short-wave approximation for thin gaps it is also shown (in an appendix) that for ideal fluids the considered helical magnetorotational instability only exists for rotation laws with negative shear. KW - plasma instabilities KW - astrophysical plasmas Y1 - 2021 U6 - https://doi.org/10.1017/S0022377821000295 SN - 1469-7807 VL - 87 IS - 2 PB - Cambridge University Press CY - London ER - TY - JOUR A1 - Eckert, Sebastian A1 - Vaz da Cruz, Vinícius A1 - Ochmann, Miguel A1 - Ahnen, Inga von A1 - Föhlisch, Alexander A1 - Huse, Nils T1 - Breaking the symmetry of pyrimidine BT - solvent effects and core-excited state dynamics JF - The journal of physical chemistry letters N2 - Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning. Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpclett.1c01865 SN - 1948-7185 VL - 12 IS - 35 SP - 8637 EP - 8643 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Norell, Jesper A1 - Eckert, Sebastian A1 - Van Kuiken, Benjamin E. A1 - Föhlisch, Alexander A1 - Odelius, Michael T1 - Ab initio simulations of complementary K-edges and solvatization effects for detection of proton transfer in aqueous 2-thiopyridone JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The nitrogen and sulfur K-edge X-ray absorption spectra of aqueous 2-thiopyridone, a model system for excited-state proton transfer in several recent time-resolved measurements, have been simulated from ab initio molecular dynamics. Spectral signatures of the local intra- and inter-molecular structure are identified and rationalized, which facilitates experimental interpretation and optimization. In particular, comparison of aqueous and gas phase spectrum simulations assesses the previously unquantified solvatization effects, where hydrogen bonding is found to yield solvatochromatic shifts up to nearly 1 eV of the main peak positions. Thereby, while each K-edge can still decisively determine the local protonation of its core-excited site, only their combined, complementary fingerprints allow separating all of the three relevant molecular forms, giving a complete picture of the proton transfer. Y1 - 2019 U6 - https://doi.org/10.1063/1.5109840 SN - 0021-9606 SN - 1089-7690 VL - 151 IS - 11 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Jay, Raphael M. A1 - Norell, Jesper A1 - Eckert, Sebastian A1 - Hantschmann, Markus A1 - Beye, Martin A1 - Kennedy, Brian A1 - Quevedo, Wilson A1 - Schlotter, William F. A1 - Dakovski, Georgi L. A1 - Minitti, Michael P. A1 - Hoffmann, Matthias C. A1 - Mitra, Ankush A1 - Moeller, Stefan P. A1 - Nordlund, Dennis A1 - Zhang, Wenkai A1 - Liang, Huiyang W. A1 - Kunnus, Kristian A1 - Kubicek, Katharina A1 - Techert, Simone A. A1 - Lundberg, Marcus A1 - Wernet, Philippe A1 - Gaffney, Kelly A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Disentangling Transient Charge Density and Metal-Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering JF - The journal of physical chemistry letters N2 - Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpclett.8b01429 SN - 1948-7185 VL - 9 IS - 12 SP - 3538 EP - 3543 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Niskanen, Johannes A1 - Fondell, Mattis A1 - Sahle, Christoph J. A1 - Eckert, Sebastian A1 - Jay, Raphael Martin A1 - Gilmore, Keith A1 - Pietzsch, Annette A1 - Dantz, Marcus A1 - Lu, Xingye A1 - McNally, Daniel E. A1 - Schmitt, Thorsten A1 - Vaz da Cruz, Vinicius A1 - Kimberg, Victor A1 - Föhlisch, Alexander A1 - Gel’mukhanov, Faris T1 - Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions JF - Proceedings of the National Academy of Sciences of the United States of America N2 - The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 +/- 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray-matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open. KW - structure of water KW - X-ray spectroscopy KW - continuous distribution model Y1 - 2019 U6 - https://doi.org/10.1073/pnas.1815701116 SN - 0027-8424 VL - 116 IS - 10 SP - 4058 EP - 4063 PB - National Acad. of Sciences CY - Washington ER - TY - JOUR A1 - Vaz da Cruz, Vinicius A1 - Eckert, Sebastian A1 - Iannuzzi, Marcella A1 - Ertan, Emelie A1 - Pietzsch, Annette A1 - Couto, Rafael C. A1 - Niskanen, Johannes A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Schmitt, Thorsten A1 - Lu, Xingye A1 - McNally, Daniel A1 - Jay, Raphael Martin A1 - Kimberg, Victor A1 - Föhlisch, Alexander A1 - Odelius, Michael T1 - Probing hydrogen bond strength in liquid water by resonant inelastic X-ray scattering JF - Nature Communications N2 - Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding. Y1 - 2019 U6 - https://doi.org/10.1038/s41467-019-08979-4 SN - 2041-1723 VL - 10 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Jay, Raphael Martin A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Miedema, Piter S. A1 - Norell, Jesper A1 - Pietzsch, Annette A1 - Quevedo, Wilson A1 - Niskanen, Johannes A1 - Kunnus, Kristjan A1 - Föhlisch, Alexander T1 - The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(II) complexes JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2′-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications. Y1 - 2018 U6 - https://doi.org/10.1039/c8cp04341h SN - 1463-9076 SN - 1463-9084 VL - 20 IS - 44 SP - 27745 EP - 27751 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Jay, Raphael Martin A1 - Fondell, Mattis A1 - Mitzner, Rolf A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - T-1 Population as the Driver of Excited-State Proton-Transfer in 2-Thiopyridone JF - Chemistry - a European journal N2 - Excited-state proton transfer (ESPT) is a fundamental process in biomolecular photochemistry, but its underlying mediators often evade direct observation. We identify a distinct pathway for ESPT in aqueous 2-thiopyridone, by employing transient N1s X-ray absorption spectroscopy and multi-configurational spectrum simulations. Photoexcitations to the singlet S-2 and S-4 states both relax promptly through intersystem crossing to the triplet T-1 state. The T-1 state, through its rapid population and near nanosecond lifetime, mediates nitrogen site deprotonation by ESPT in a secondary intersystem crossing to the S-0 potential energy surface. This conclusively establishes a dominant ESPT pathway for the system in aqueous solution, which is also compatible with previous measurements in acetonitrile. Thereby, the hitherto open questions of the pathway for ESPT in the compound, including its possible dependence on excitation wavelength and choice of solvent, are resolved. KW - excited-state proton-transfer KW - intersystem crossing KW - nitrogen KW - photochemistry KW - X-ray absorption Y1 - 2019 U6 - https://doi.org/10.1002/chem.201804166 SN - 0947-6539 SN - 1521-3765 VL - 25 IS - 7 SP - 1733 EP - 1739 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Jay, Raphael Martin A1 - Eckert, Sebastian A1 - Vaz da Cruz, Vinicius A1 - Fondell, Mattis A1 - Mitzner, Rolf A1 - Föhlisch, Alexander T1 - Covalency-driven preservation of local charge densities in a metal-to-ligand charge-transfer excited iron photosensitizer JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Charge-density rearrangements after metal-to-ligand charge-transfer excitation in an iron photosensitizer are investigated by R. M Jay, A. Fohlisch et al. in their Communication (DOI: 10.1002/anie.201904761). By using time-resolved X-ray absorption spectroscopy, surprising covalency-effects are revealed that inhibit charge-separation at the intra-molecular level. Furthermore, the underlying mechanism is proposed to be generally in effect for all commonly used photosensitizers in light-harvesting applications, which challenges the common perception of electronic charge-transfer. KW - charge-transfer KW - density functional calculations KW - iron KW - photochemistry KW - X-ray absorption spectroscopy Y1 - 2019 U6 - https://doi.org/10.1002/anie.201904761 SN - 1433-7851 SN - 1521-3773 VL - 58 IS - 31 SP - 10742 EP - 10746 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Eckert, Sebastian A1 - Vaz da Cruz, Vinicius A1 - Ertan, Emelie A1 - Ignatova, Nina A1 - Polyutov, Sergey A1 - Couto, Rafael C. A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Kennedy, Brian A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - One-dimensional cuts through multidimensional potential-energy surfaces by tunable x rays JF - Physical review : A, Atomic, molecular, and optical physics N2 - The concept of the potential-energy surface (PES) and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to (near) degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close-lying vibrational levels. We show here that resonant inelastic x-ray scattering (RIXS) constitutes an ideal probe for revealing one-dimensional cuts through the ground-state PES of molecular systems, even far away from the equilibrium geometry, where the independent-mode picture is broken. We strictly link the center of gravity of close-lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one-dimensional Hamiltonian along the propagation coordinate of the core-excited wave packet. This concept, combined with directional and site selectivity of the core-excited states, allows us to experimentally extract cuts through the ground-state PES along three complementary directions for the showcase H2O molecule. Y1 - 2018 U6 - https://doi.org/10.1103/PhysRevA.97.053410 SN - 2469-9926 SN - 2469-9934 VL - 97 IS - 5 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Pietzsch, Annette A1 - Niskanen, Johannes A1 - Vaz da Cruz, Vinicius A1 - Büchner, Robby A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Jay, Raphael Martin A1 - Lu, Xingye A1 - McNally, Daniel A1 - Schmitt, Thorsten A1 - Föhlisch, Alexander T1 - Cuts through the manifold of molecular H2O potential energy surfaces in liquid water at ambient conditions JF - Proceedings of the National Academy of Sciences of the United States of America N2 - The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H2O molecular moieties. This is mirrored in a manifold of the H2O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H2O symmetric normal mode and the local asymmetric O-H bond coordinate up to 1 and 1.5 angstrom, respectively. The comparison of the single H2O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H2O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O-H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen ls to 4a(1) resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2b(2) resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H2O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O-H, H-H, and O-O correlation lengths from neutron scattering. KW - water KW - potential ene rgy surface KW - RIXS Y1 - 2022 U6 - https://doi.org/10.1073/pnas.2118101119 SN - 1091-6490 VL - 119 IS - 28 PB - National Acad. of Sciences CY - Washington, DC ER - TY - JOUR A1 - Jay, Raphael M. A1 - Vaz da Cruz, Vinicius A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Mitzner, Rolf A1 - Föhlisch, Alexander T1 - Probing solute-solvent interactions of transition metal complexes using L-edge absorption spectroscopy JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - In order to tailor solution-phase chemical reactions involving transition metal complexes, it is critical to understand how their valence electronic charge distributions are affected by the solution environment. Here, solute-solvent interactions of a solvatochromic mixed-ligand iron complex were investigated using X-ray absorption spectroscopy at the transition metal L-2,L-3-edge. Due to the selectivity of the corresponding core excitations to the iron 3d orbitals, the method grants direct access to the valence electronic structure around the iron center and its response to interactions with the solvent environment. A linear increase of the total L-2,L-3-edge absorption cross section as a function of the solvent Lewis acidity is revealed. The effect is caused by relative changes in different metal-ligand-bonding channels, which preserve local charge densities while increasing the density of unoccupied states around the iron center. These conclusions are corroborated by a combination of molecular dynamics and spectrum simulations based on time-dependent density functional theory. The simulations reproduce the spectral trends observed in the X-ray but also optical absorption experiments. Our results underscore the importance of solute-solvent interactions when aiming for an accurate description of the valence electronic structure of solvated transition metal complexes and demonstrate how L-2,L-3-edge absorption spectroscopy can aid in understanding the impact of the solution environment on intramolecular covalency and the electronic charge distribution. KW - basis-sets KW - charge-transfer KW - density KW - dynamics KW - electron localization KW - iron KW - solvation KW - spin-crossover KW - tranfer excited-state KW - x-ray-absorption Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpcb.0c00638 SN - 1520-6106 SN - 1520-5207 VL - 124 IS - 27 SP - 5636 EP - 5645 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Couto, Rafael C. A1 - Cruz, Vinicius V. A1 - Ertan, Emelie A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Kennedy, Brian A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Guimaraes, Freddy F. A1 - Agren, Hans A1 - Odelius, Michael A1 - Kimberg, Victor A1 - Föhlisch, Alexander T1 - Selective gating to vibrational modes through resonant X-ray scattering JF - Nature Communications N2 - The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations. Y1 - 2017 U6 - https://doi.org/10.1038/ncomms14165 SN - 2041-1723 VL - 8 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Jay, Raphael M. A1 - Eckert, Sebastian A1 - Mitzner, Rolf A1 - Fondell, Mattis A1 - Föhlisch, Alexander T1 - Quantitative evaluation of transient valence orbital occupations in a 3d transition metal complex as seen from the metal and ligand perspective JF - Chemical physics letters N2 - It is demonstrated for the case of photo-excited ferrocyanide how time-resolved soft X-ray absorption spectroscopy in transmission geometry at the ligand K-edge and metal L-3-edge provides quantitatively equivalent valence electronic structure information, where signatures of photo-oxidation are assessed locally at the metal as well as the ligand. This allows for a direct and independent quantification of the number of photo-oxidized molecules at two soft X-ray absorption edges highlighting the sensitivity of X-ray absorption spectroscopy to the valence orbital occupation of 3d transition metal complexes throughout the soft X-ray range. KW - iron cyanides KW - photochemistry KW - soft X-ray absorption Y1 - 2020 U6 - https://doi.org/10.1016/j.cplett.2020.137681 SN - 0009-2614 SN - 1873-4448 VL - 754 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Mascarenhas, Eric Johnn A1 - Fondell, Mattis A1 - Büchner, Robby A1 - Eckert, Sebastian A1 - Vaz da Cruz, Vinícius A1 - Föhlisch, Alexander T1 - Photo-induced ligand substitution of Cr(CO)(6) in 1-pentanol probed by time resolved X-ray absorption spectroscopy JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Cr(CO)(6) was investigated by X-ray absorption spectroscopy. The spectral signature at the metal edge provides information about the back-bonding of the metal in this class of complexes. Among the processes it participates in is ligand substitution in which a carbonyl ligand is ejected through excitation to a metal to ligand charge transfer (MLCT) band. The unsaturated carbonyl Cr(CO)(5) is stabilized by solution media in square pyramidal geometry and further reacts with the solvent. Multi-site-specific probing after photoexcitation was used to investigate the ligand substitution photoreaction process which is a common first step in catalytic processes involving metal carbonyls. The data were analysed with the aid of TD-DFT computations for different models of photoproducts and signatures for ligand rearrangement after substitution were found. The rearrangement was found to occur in about 790 ps in agreement with former studies of the photoreaction. Y1 - 2022 U6 - https://doi.org/10.1039/d1cp05834g SN - 1463-9076 SN - 1463-9084 VL - 24 IS - 30 SP - 17979 EP - 17985 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Vaz da Cruz, Vinicius A1 - Büchner, Robby A1 - Fondell, Mattis A1 - Pietzsch, Annette A1 - Eckert, Sebastian A1 - Föhlisch, Alexander T1 - Targeting individual tautomers in equilibrium by resonant inelastic X-ray scattering JF - The journal of physical chemistry letters N2 - Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the pi and sigma manifolds at the proton-transfer site. KW - Equilibrium KW - Molecular structure KW - Molecules KW - Nitrogen KW - Solvents Y1 - 2022 U6 - https://doi.org/10.1021/acs.jpclett.1c03453 SN - 1948-7185 VL - 13 IS - 10 SP - 2459 EP - 2466 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Eckert, Sebastian A1 - Mascarenhas, Eric Johnn A1 - Mitzner, Rolf A1 - Jay, Raphael Martin A1 - Pietzsch, Annette A1 - Fondell, Mattis A1 - Vaz da Cruz, Vinicius A1 - Föhlisch, Alexander T1 - From the free ligand to the transition metal complex BT - FeEDTA(-) formation seen at ligand K-Edges JF - Inorganic chemistry N2 - Chelating agents are an integral part of transition metal complex chemistry with broad biological and industrial relevance. The hexadentate chelating agent ethylenediaminetetraacetic acid (EDTA) has the capability to bind to metal ions at its two nitrogen and four of its carboxylate oxygen sites. We use resonant inelastic X-ray scattering at the 1s absorption edge of the aforementioned elements in EDTA and the iron(III)-EDTA complex to investigate the impact of the metal-ligand bond formation on the electronic structure of EDTA. Frontier orbital distortions, occupation changes, and energy shifts through metal- ligand bond formation are probed through distinct spectroscopic signatures. KW - Energy KW - Ligands KW - Metals KW - Nitrogen KW - Oxygen Y1 - 2022 U6 - https://doi.org/10.1021/acs.inorgchem.2c00789 SN - 0020-1669 SN - 1520-510X VL - 61 IS - 27 SP - 10321 EP - 10328 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Aranson, Igor S. A1 - Pikovskij, Arkadij T1 - Confinement and collective escape of active particles JF - Physical review letters N2 - Active matter broadly covers the dynamics of self-propelled particles. While the onset of collective behavior in homogenous active systems is relatively well understood, the effect of inhomogeneities such as obstacles and traps lacks overall clarity. Here, we study how interacting, self-propelled particles become trapped and released from a trap. We have found that captured particles aggregate into an orbiting condensate with a crystalline structure. As more particles are added, the trapped condensates escape as a whole. Our results shed light on the effects of confinement and quenched disorder in active matter. Y1 - 2022 U6 - https://doi.org/10.1103/PhysRevLett.128.108001 SN - 0031-9007 SN - 1079-7114 SN - 1092-0145 VL - 128 IS - 10 PB - American Physical Society CY - College Park, Md. ER - TY - JOUR A1 - Vaz da Cruz, Vinícius A1 - Ignatova, Nina A1 - Couto, Rafael A1 - Fedotov, Daniil A1 - Rehn, Dirk R. A1 - Savchenko, Viktoriia A1 - Norman, Patrick A1 - Ågren, Hans A1 - Polyutov, Sergey A1 - Niskanen, Johannes A1 - Eckert, Sebastian A1 - Jay, Raphael Martin A1 - Fondell, Mattis A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Föhlisch, Alexander A1 - Odelius, Michael A1 - Kimberg, Victor A1 - Gel’mukhanov, Faris T1 - Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - We report on a combined theoretical and experimental study of core-excitation spectra of gas and liquid phase methanol as obtained with the use of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The electronic transitions are studied with computational methods that include strict and extended second-order algebraic diagrammatic construction [ADC(2) and ADC(2)-x], restricted active space second-order perturbation theory, and time-dependent density functional theory-providing a complete assignment of the near oxygen K-edge XAS. We show that multimode nuclear dynamics is of crucial importance for explaining the available experimental XAS and RIXS spectra. The multimode nuclear motion was considered in a recently developed "mixed representation" where dissociative states and highly excited vibrational modes are accurately treated with a time-dependent wave packet technique, while the remaining active vibrational modes are described using Franck-Condon amplitudes. Particular attention is paid to the polarization dependence of RIXS and the effects of the isotopic substitution on the RIXS profile in the case of dissociative core-excited states. Our approach predicts the splitting of the 2a RIXS peak to be due to an interplay between molecular and pseudo-atomic features arising in the course of transitions between dissociative core- and valence-excited states. The dynamical nature of the splitting of the 2a peak in RIXS of liquid methanol near pre-edge core excitation is shown. The theoretical results are in good agreement with our liquid phase measurements and gas phase experimental data available from the literature. (C) 2019 Author(s). Y1 - 2019 U6 - https://doi.org/10.1063/1.5092174 SN - 0021-9606 SN - 1089-7690 VL - 150 IS - 23 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Maiti, Snehanshu A1 - Makwana, Kirit A1 - Zhang, Heshou A1 - Yan, Huirong T1 - Cosmic-ray transport in magnetohydrodynamic turbulence JF - The astrophysical journal : an international review of spectroscopy and astronomical physics / part 1 N2 - This paper studies cosmic-ray (CR) transport in magnetohydrodynamic (MHD) turbulence. CR transport is strongly dependent on the properties of the magnetic turbulence. We perform test particle simulations to study the interactions of CR with both total MHD turbulence and decomposed MHD modes. The spatial diffusion coefficients and the pitch angle scattering diffusion coefficients are calculated from the test particle trajectories in turbulence. Our results confirm that the fast modes dominate the CR propagation, whereas Alfven and slow modes are much less efficient and have shown similar pitch-angle scattering rates. We investigate the cross field transport on large and small scales. On large/global scales, normal diffusion is observed and the diffusion coefficient is suppressed by M-A(zeta) compared to the parallel diffusion coefficients, with zeta closer to 4 in Alfven modes than that in total turbulence, as theoretically expected. For the CR transport on scales smaller than the turbulence injection scale, both the local and global magnetic reference frames are adopted. Superdiffusion is observed on such small scales in all the cases. Particularly, CR transport in Alfven modes show clear Richardson diffusion in the local reference frame. The diffusion transitions smoothly from the Richardson's one with index 1.5 to normal diffusion as the particle mean free path decreases from lambda(parallel to) >> L to lambda(parallel to) << L, where L is the injection/coherence length of turbulence. Our results have broad applications to CRs in various astrophysical environments. Y1 - 2022 U6 - https://doi.org/10.3847/1538-4357/ac46c8 SN - 1538-4357 VL - 926 IS - 1 PB - Institute of Physics Publ. CY - London ER - TY - JOUR A1 - Ochmann, Miguel A1 - Vaz da Cruz, Vinicius A1 - Eckert, Sebastian A1 - Huse, Nils A1 - Föhlisch, Alexander T1 - R-Group stabilization in methylated formamides observed by resonant inelastic X-ray scattering JF - Chemical communications: ChemComm N2 - The inherent stability of methylated formamides is traced to a stabilization of the deep-lying sigma-framework by resonant inelastic X-ray scattering at the nitrogen K-edge. Charge transfer from the amide nitrogen to the methyl groups underlie this stabilization mechanism that leaves the aldehyde group essentially unaltered and explains the stability of secondary and tertiary amides. Y1 - 2022 U6 - https://doi.org/10.1039/d2cc00053a SN - 1359-7345 SN - 1364-548X VL - 58 IS - 63 SP - 8834 EP - 8837 PB - The Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Sandev, Trifce A1 - Domazetoski, Viktor A1 - Kocarev, Ljupco A1 - Metzler, Ralf A1 - Chechkin, Aleksei T1 - Heterogeneous diffusion with stochastic resetting JF - Journal of physics : A, Mathematical and theoretical N2 - We study a heterogeneous diffusion process (HDP) with position-dependent diffusion coefficient and Poissonian stochastic resetting. We find exact results for the mean squared displacement and the probability density function. The nonequilibrium steady state reached in the long time limit is studied. We also analyse the transition to the non-equilibrium steady state by finding the large deviation function. We found that similarly to the case of the normal diffusion process where the diffusion length grows like t (1/2) while the length scale xi(t) of the inner core region of the nonequilibrium steady state grows linearly with time t, in the HDP with diffusion length increasing like t ( p/2) the length scale xi(t) grows like t ( p ). The obtained results are verified by numerical solutions of the corresponding Langevin equation. KW - heterogeneous diffusion KW - Fokker-Planck equation KW - Langevin equation KW - stochastic resetting KW - nonequilibrium stationary state KW - large deviation function Y1 - 2022 U6 - https://doi.org/10.1088/1751-8121/ac491c SN - 1751-8113 SN - 1751-8121 VL - 55 IS - 7 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - He, Yushuang A1 - Wang, Feipeng A1 - He, Li A1 - Wang, Qiang A1 - Li, Jian A1 - Qian, Yihua A1 - Gerhard, Reimund A1 - Plath, Ronald T1 - An insight Into the role of Nano-Alumina on DC Flashover-Resistance and surface charge variation of Epoxy Nanocomposites JF - IEEE transactions on dielectrics and electrical insulation N2 - The addition of nano-Al2O3 has been shown to enhance the breakdown voltage of epoxy resin, but its flashover results appeared with disputation. This work concentrates on the surface charge variation and dc flashover performance of epoxy resin with nano-Al2O3 doping. The dispersion of nano-Al2O3 in epoxy is characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The dc flashover voltages of samples under either positive or negative polarity are measured with a finger-electrode system, and the surface charge variations before and after flashovers were identified from the surface potential mapping. The results evidence that nano-Al2O3 would lead to a 16.9% voltage drop for the negative flashovers and a 6.8% drop for positive cases. It is found that one-time flashover clears most of the accumulated surface charges, regardless of positive or negative. As a result, the ground electrode is neighbored by an equipotential zone enclosed with low-density heterocharges. The equipotential zone tends to be broadened after 20 flashovers. The nano-Al2O3 is noticed as beneficial to downsize the equipotential zone due to its capability on charge migration, which is reasonable to maintain flashover voltage at a high level after multiple flashovers. Hence, nano-Al2O3 plays a significant role in improving epoxy with high resistance to multiple flashovers. KW - surface morphology KW - Epoxy resins KW - Electric potential KW - Surface treatment KW - Doping KW - Epoxy resin KW - multiple KW - flashover KW - nanocomposite KW - surface charge Y1 - 2022 U6 - https://doi.org/10.1109/TDEI.2022.3173510 SN - 1070-9878 SN - 1558-4135 VL - 29 IS - 3 SP - 1022 EP - 1029 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Wang, Feipeng A1 - Zhang, Zheng A1 - Yan, Yuyang A1 - Shen, Zijia A1 - Wang, Qiang A1 - Gerhard, Reimund T1 - Surface reconstruction on electro-spun PVA/PVP nanofibers by water evaporation JF - Nanomaterials N2 - Tailoring the secondary surface morphology of electro-spun nanofibers has been highly desired, as such delicate structures equip nanofibers with distinct functions. Here, we report a simple strategy to directly reconstruct the surface of polyvinyl alcohol/polyvinylpyrrolidone (PVA/PVP) nanofibers by water evaporation. The roughness and diameter of the nanofibers depend on the temperature during vacuum drying. Surface changes of the nanofibers from smooth to rough were observed at 55 degrees C, with a significant drop in nanofiber diameter. We attribute the formation of the secondary surface morphology to the intermolecular forces in the water vapor, including capillary and the compression forces, on the basis of the results from the Fourier-transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy. The strategy is universally effective for various electro-spun polymer nanofibers, thus opening up avenues toward more detailed and sophisticated structure design and implementation for nanofibers. KW - surface reconstruction KW - intermolecular force KW - surface-roughened KW - nanofiber Y1 - 2022 U6 - https://doi.org/10.3390/nano12050797 SN - 2079-4991 VL - 12 IS - 5 PB - MDPI CY - Basel ER - TY - JOUR A1 - Arya, Pooja A1 - Jelken, Joachim A1 - Feldmann, David A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Light driven diffusioosmotic repulsion and attraction of colloidal particles JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - In this paper, we introduce the phenomenon of light driven diffusioosmotic long-range attraction and repulsion of porous particles under irradiation with UV light. The change in the inter-particle interaction potential is governed by flow patterns generated around single colloids and results in reversible aggregation or separation of the mesoporous silica particles that are trapped at a solid surface. The range of the interaction potential extends to several times the diameter of the particle and can be adjusted by varying the light intensity. The "fuel" of the process is a photosensitive surfactant undergoing photo-isomerization from a more hydrophobic trans-state to a rather hydrophilic cis-state. The surfactant has different adsorption affinities to the particles depending on the isomerization state. The trans-isomer, for example, tends to accumulate in the negatively charged pores of the particles, while the cis-isomer prefers to remain in the solution. This implies that when under UV irradiation cis-isomers are being formed within the pores, they tend to diffuse out readily and generate an excess concentration near the colloid's outer surface, ultimately resulting in the initiation of diffusioosmotic flow. The direction of the flow depends strongly on the dynamic redistribution of the fraction of trans- and cis-isomers near the colloids due to different kinetics of photo-isomerization within the pores as compared to the bulk. The unique feature of the mechanism discussed in the paper is that the long-range mutual repulsion but also the attraction can be tuned by convenient external optical stimuli such as intensity so that a broad variety of experimental situations for manipulation of a particle ensemble can be realized. Y1 - 2020 U6 - https://doi.org/10.1063/5.0007556 SN - 0021-9606 SN - 1089-7690 VL - 152 IS - 19 PB - American Institute of Physics CY - Melville, NY ER - TY - JOUR A1 - Feldmann, David A1 - Arya, Pooja A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Santer, Svetlana T1 - Light-driven motion of self-propelled porous Janus particles JF - Applied physics letters N2 - We introduce a versatile mechanism of light-driven self-propelled motion applied to porous Janus-type particles. The mechanism is based on the generation of local light-driven diffusio-osmotic (l-LDDO) flow around each single porous particle subjected to suitable irradiation conditions. The photosensitivity is introduced by a cationic azobenzene containing surfactant, which undergoes a photoisomerization reaction from a more hydrophobic trans-state to a rather hydrophilic cis-state under illumination with light. The negatively charged porous silica particles are dispersed in a corresponding aqueous solution and absorb molecules in their trans-state but expel them in their cis-state. During illumination with blue light triggering both trans-cis and cis-trans isomerization at the same time, the colloids start to move due to the generation of a steady-state diffusive flow of cis-isomers out of and trans-isomers into the particle. This is because a hemi-spherical metal cap partially sealing the colloid breaks the symmetry of the otherwise radially directed local flow around the particle, leading to self-propelled motion. Janus particles exhibit superdiffusive motion with a velocity of similar to 0.5 mu m/s and a persistence length of ca. 50 mu m, confined to microchannels the direction can be maintained up to 300 mu m before rotational diffusion reverts it. Particles forming dimers of different shapes can be made to travel along circular trajectories. The unique feature of this mechanism is that the strength of self-propulsion can be tuned by convenient external optical stimuli (intensity and irradiation wavelength) such that a broad variety of experimental situations can be realized in a spatiotemporal way and in situ. Y1 - 2019 U6 - https://doi.org/10.1063/1.5129238 SN - 0003-6951 SN - 1077-3118 VL - 115 IS - 26 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Jelken, Joachim A1 - Henkel, Carsten A1 - Santer, Svetlana T1 - Solving an old puzzle: fine structure of diffraction spots from an azo-polymer surface relief grating JF - Applied physics : B, Lasers and optics N2 - We report on the experimental and theoretical interpretation of the diffraction of a probe beam during inscription of a surface relief grating with an interference pattern into a photo-responsive polymer film. For this, we developed a set-up allowing for the simultaneous recording of the diffraction efficiency (DE), the fine structure of the diffraction spot and the topographical changes, in situ and in real time while the film is irradiated. The time dependence of the DE, as the surface relief deepens, follows a Bessel function exhibiting maxima and minima. The size of the probe beam relative to the inscribed grating (i.e., to the size of the writing beams) matters and has to be considered for the interpretation of the DE signal. It is also at the origin of a fine structure within the diffraction spot where ring-shaped features appear once an irradiation time corresponding to the first maximum of the DE has been exceeded. Y1 - 2019 U6 - https://doi.org/10.1007/s00340-019-7331-8 SN - 0946-2171 SN - 1432-0649 VL - 125 IS - 11 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Schimka, Selina A1 - Klier, Dennis Tobias A1 - de Guerenu, Anna Lopez A1 - Bastian, Philipp A1 - Lomadze, Nino A1 - Kumke, Michael Uwe A1 - Santer, Svetlana T1 - Photo-isomerization of azobenzene containing surfactants induced by near-infrared light using upconversion nanoparticles as mediator JF - Journal of physics : Condensed matter N2 - Here we report on photo-isomerization of azobenzene containing surfactants induced during irradiation with near-infrared (NIR) light in the presence of upconversion nanoparticles (UCNPs) acting as mediator. The surfactant molecule consists of charged head group and hydrophobic tail with azobenzene group incorporated in alkyl chain. The azobenzene group can be reversible photo-isomerized between two states: trans- and cis- by irradiation with light of an appropriate wavelength. The trans-cis photo-isomerization is induced by UV light, while cis-trans isomerization proceeds either thermally in darkness, or can be accelerated by exposure to illumination with a longer wavelength typically in a blue/green range. We present the application of lanthanide doped UCNPs to successfully switch azobenzene containing surfactants from cis to trans conformation in bulk solution using NIR light. Using Tm-3(+) or Er-3(+) as activator ions, the UCNPs provide emissions in the spectral range of 450 nm < lambda(em) < 480 nm (for Tm-3(+), three and four photon induced emission) or 525 nm < lambda(em) < 545 nm (for Er-3(+), two photon induced emission), respectively. Especially for UCNPs containing Tm-3(+) a good overlap of the emissions with the absorption bands of the azobenzene is present. Under illumination of the surfactant solution with NIR light (lambda(ex) = 976 nm) in the presence of the Tm-3(+)-doped UCNPs, the relaxation time of cis-trans photo-isomerization was increased by almost 13 times compared to thermally induced isomerization. The influence of thermal heating due to the irradiation using NIR light was shown to be minor for solvents not absorbing in NIR spectral range (e.g. CHCl3) in contrast to water, which shows a distinct absorption in the NIR. KW - upconversion nanoparticles KW - azobenzene containing surfactants KW - kinetic of cis-trans isomerization Y1 - 2019 U6 - https://doi.org/10.1088/1361-648X/aafcfa SN - 0953-8984 SN - 1361-648X VL - 31 IS - 12 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Jelken, Joachim A1 - Pandiyarajan, Chinnayan Kannan A1 - Genzer, Jan A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Fabrication of flexible hydrogel sheets featuring periodically spaced circular holes with continuously adjustable size in realtime JF - ACS applied materials & interfaces N2 - We report on the formation of stimuli-responsive structured hydrogel thin films whose pattern geometry can be adjusted on demand and tuned reversibly by varying solvent quality or by changing temperature. The hydrogel films, similar to 100 nm in thickness, were prepared by depositing layers of random copolymers comprising N-isopropylacrylamide and ultraviolet (UV)-active methacryloyloxybenzophenone units onto solid substrates. A two-beam interference pattern technique was used to cross-link the selected areas of the film; any unreacted material was extracted using ethanol after UV light-assisted cross-linking. In this way, we produced nanoholes, perfectly ordered structures with a narrow size distribution, negligible tortuosity, adjustable periodicity, and a high density. The diameter of the circular holes ranged from a few micrometers down to several tens of nanometers; the hole periodicity could be adjusted readily by changing the optical period of the UV interference pattern. The holes were reversibly closed and opened by swelling/deswelling the polymer networks in the presence of ethanol and water, respectively, at various temperatures. The reversible regulation of the hole diameter can be repeated many times within a few seconds. The hydrogel sheet with circular holes periodically arranged may also be transferred onto different substrates and be employed as tunable templates for the deposition of desired substances. KW - photosensitive polymers KW - PNIPAm KW - hydrogels KW - UV cross-linking KW - stimuli-responsive structured polymer films KW - azobenzene-containing molecules Y1 - 2018 U6 - https://doi.org/10.1021/acsami.8b09580 SN - 1944-8244 VL - 10 IS - 36 SP - 30844 EP - 30851 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Loebner, Sarah A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Koch, Markus A1 - Guskova, Olga A1 - Saphiannikova, Marina A1 - Santer, Svetlana T1 - Light-Induced Deformation of Azobenzene-Containing Colloidal Spheres BT - Calculation and Measurement of Opto-Mechanical Stresses JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 mu m in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [J. Phys. Chem. Lett. 2017, 8, 1094], we calculated the optomechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpcb.7b11644 SN - 1520-6106 VL - 122 IS - 6 SP - 2001 EP - 2009 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schimka, Selina A1 - Lomadze, Nino A1 - Rabe, Maren A1 - Kopyshev, Alexey A1 - Lehmann, Maren A1 - von Klitzing, Regine A1 - Rumyantsev, Artem M. A1 - Kramarenko, Elena Yu. A1 - Santer, Svetlana T1 - Photosensitive microgels containing azobenzene surfactants of different charges JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans- state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine. Y1 - 2016 U6 - https://doi.org/10.1039/c6cp04555c SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 108 EP - 117 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Jelken, Joachim A1 - Henkel, Carsten A1 - Santer, Svetlana T1 - Formation of half-period surface relief gratings in azobenzene containing polymer films JF - Applied physics : B, Lasers and optics N2 - We study the peculiar response of photo-sensitive polymer films irradiated with a certain type of interference pattern where one interfering beam is S-polarized, while the second one is P-polarized. The polymer film, although in a glassy state, deforms following the local polarization distribution of the incident light, and a surface relief grating (SRG) appears whose period is half the optical one. All other types of interference patterns result in the matching of both periods. The topographical response is triggered by the alignment of photo-responsive azobenzene containing polymer side chains orthogonal to the local electrical field, resulting in a bulk birefringence grating (BBG). We investigate the process of dual grating formation (SRG and BBG) in a polymer film utilizing a dedicated set-up that combines probe beam diffraction and atomic force microscopy (AFM) measurements, and permits acquiring in situ and in real-time information about changes in local topography and birefringence. We find that the SRG maxima appear at the positions of linearly polarized light (tilted by 45 degrees relative to the grating vector), causing the formation of the half-period topography. This permits to inscribe symmetric and asymmetric topography gratings with sub-wavelength period, while changing only slightly the polarization of one of the interfering beams. We demonstrate an easy generation of sawtooth profiles (blazed gratings) with adjustable shape. With these results, we have taken a significant step in understanding the photo-induced deformation of azo-polymer films. Y1 - 2020 U6 - https://doi.org/10.1007/s00340-020-07500-w SN - 0946-2171 SN - 1432-0649 VL - 126 IS - 9 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Arya, Pooja A1 - Jelken, Joachim A1 - Lomadze, Nino A1 - Santer, Svetlana A1 - Bekir, Marek T1 - Kinetics of photo-isomerization of azobenzene containing surfactants JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry N2 - We report on photoisomerization kinetics of azobenzene containing surfactants in aqueous solution. The surfactant molecule consists of a positively charged trimethylammonium bromide head group, a hydrophobic spacer connecting via 6 to 10 CH2 groups to the azobenzene unit, and the hydrophobic tail of 1 and 3CH(2) groups. Under exposure to light, the azobenzene photoisomerizes from more stable trans- to metastable cis-state, which can be switched back either thermally in dark or by illumination with light of a longer wavelength. The surfactant isomerization is described by a kinetic model of a pseudo first order reaction approaching equilibrium, where the intensity controls the rate of isomerization until the equilibrated state. The rate constants of the trans-cis and cis-trans photoisomerization are calculated as a function of several parameters such as wavelength and intensity of light, the surfactant concentration, and the length of the hydrophobic tail. The thermal relaxation rate from cis- to trans-state is studied as well. The surfactant isomerization shows a different kinetic below and above the critical micellar concentration of the trans isomer due to steric hindrance within the densely packed micelle but does not depend on the spacer length. KW - genomic DNA conformation KW - water-interface KW - light photocontrol KW - driven KW - manipulation KW - photoisomerization KW - molecules Y1 - 2020 U6 - https://doi.org/10.1063/1.5135913 SN - 0021-9606 SN - 1089-7690 VL - 152 IS - 2 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Muraveva, Valeriia A1 - Bekir, Marek A1 - Lomadze, Nino A1 - Großmann, Robert A1 - Beta, Carsten A1 - Santer, Svetlana T1 - Interplay of diffusio- and thermo-osmotic flows generated by single light stimulus JF - Applied physics letters N2 - Flow control is a highly relevant topic for micromanipulation of colloidal particles in microfluidic applications. Here, we report on a system that combines two-surface bound flows emanating from thermo-osmotic and diffusio-osmotic mechanisms. These opposing flows are generated at a gold surface immersed into an aqueous solution containing a photo-sensitive surfactant, which is irradiated by a focused UV laser beam. At low power of incoming light, diffusio-osmotic flow due to local photo-isomerization of the surfactant dominates, resulting in a flow pattern oriented away from the irradiated area. In contrast, thermo-osmotic flow takes over due to local heating of the gold surface at larger power, consequently inducing a flow pointing toward the hotspot. In this way, this system allows one to reversibly switch from outward to inward liquid flow with an intermittent range of zero flow at which tracer particles undergo thermal motion by just tuning the laser intensity only. Our work, thus, demonstrates an optofluidic system for flow generation with a high degree of controllability that is necessary to transport particles precisely to desired locations, thereby opening innovative possibilities to generate advanced microfluidic applications. Y1 - 2022 U6 - https://doi.org/10.1063/5.0090229 SN - 0003-6951 SN - 1077-3118 VL - 120 IS - 23 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Silanteva, Irina A. A1 - Komolkin, Andrei A1 - Mamontova, Veronika V. A1 - Vorontsov-Velyaminov, Pavel N. A1 - Santer, Svetlana A1 - Kasyanenko, Nina A. T1 - Some features of surfactant organization in DNA solutions at various NaCl concentrations JF - ACS omega / American Chemical Society N2 - The photosensitive azobenzene-containing surfactant C-4-Azo-OC(6)TMAB is a promising agent for reversible DNA packaging in a solution. The simulation of the trans-isomer surfactant organization into associates in a solution with and without salt as well as its binding to DNA at different NaCl concentrations was carried out by molecular dynamics. Experimental data obtained by spectral and hydrodynamic methods were used to verify the results of simulation. It was shown that head-to-tail aggregates with close to antiparallel orientation of surfactant molecules were formed at certain NaCl and surfactant concentrations (below critical micelle concentration). Such aggregates have two positively charged ends, and therefore, they can be attracted to negatively charged DNA phosphates far located along the chain, as well as those that belong to different molecules. This contributes to the formation of intermolecular DNA-DNA contacts, and this way, the experimentally observed precipitation of DNA can be explained. Y1 - 2020 U6 - https://doi.org/10.1021/acsomega.0c01850 SN - 2470-1343 VL - 5 IS - 29 SP - 18234 EP - 18243 PB - ACS Publications CY - Washington ER - TY - JOUR A1 - Malyar, Ivan V. A1 - Gorin, Dmitry A. A1 - Santer, Svetlana A1 - Stetsyura, Svetlana V. T1 - Photo-assisted adsorption of gold nanoparticles onto a silicon substrate JF - Applied physics letters N2 - We report on a photo-assisted adsorption of gold nanoparticles on a silicon substrate studied using atomic-force microscopy and secondary ion mass-spectrometry. Depending on a silicon conductivity type (n-Si or p-Si), the amount of photo-assisted adsorbed gold nanoparticles either increases (n-Si) or decreases (p-Si) on irradiation. In addition, the impacts of a cationic polyelectrolyte monolayer and adsorption time were also revealed. The polyelectrolyte layer enhances the adsorption of the gold nanoparticles but decreases the influence of light. The results of the photo-assisted adsorption on two types of silicon wafer were explained by electron processes at the substrate/solution interface. This work was supported by the German-Russian Interdisciplinary Science Center (G-RISC) funded by the German Federal Foreign Office via the German Academic Exchange Service (DAAD), Project No. P-2014b-1, and Russian foundation for basic research, Project No. 16-08-00524_a. Y1 - 2017 U6 - https://doi.org/10.1063/1.4979082 SN - 0003-6951 SN - 1077-3118 VL - 110 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Simonova, Maria A1 - Ivanov, Ivan A1 - Meleshko, Tamara A1 - Kopyshev, Alexey A1 - Santer, Svetlana A1 - Yakimansky, Alexander A1 - Filippov, Alexander T1 - Self-assembly of molecular brushes with polyimide backbone and amphiphilic block copolymer side chains in selective solvents JF - Polymers N2 - Three-component molecular brushes with a polyimide backbone and amphiphilic block copolymer side chains with different contents of the "inner" hydrophilic (poly(methacrylic acid)) and "outer" hydrophobic (poly(methyl methacrylate)) blocks were synthesized and characterized by molecular hydrodynamics and optics methods in solutions of chloroform, dimethylformamide, tetrahydrofuran and ethanol. The peculiarity of the studied polymers is the amphiphilic structure of the grafted chains. The molar masses of the molecular brushes were determined by static and dynamic light scattering in chloroform in which polymers form molecularly disperse solutions. Spontaneous self-assembly of macromolecules was detected in dimethylformamide, tetrahydrofuran and ethanol. The aggregates size depended on the thermodynamic quality of the solvent as well as on the macromolecular architectural parameters. In dimethylformamide and tetrahydrofuran, the distribution of hydrodynamic radii of aggregates was bimodal, while in ethanol, it was unimodal. Moreover, in ethanol, an increase in the poly(methyl methacrylate) content caused a decrease in the hydrodynamic radius of aggregates. A significant difference in the nature of the blocks included in the brushes determines the selectivity of the used solvents, since their thermodynamic quality with respect to the blocks is different. The macromolecules of the studied graft copolymers tend to self-organization in selective solvents with formation of a core-shell structure with an insoluble solvophobic core surrounded by the solvophilic shell of side chains. KW - molecular brushes KW - amphiphilic side chains KW - molecular hydrodynamics and KW - optics KW - conformational and hydrodynamic characteristics KW - aggregation Y1 - 2020 U6 - https://doi.org/10.3390/polym12122922 SN - 2073-4360 VL - 12 IS - 12 PB - MDPI CY - Basel ER - TY - JOUR A1 - Umlandt, Maren A1 - Feldmann, David A1 - Schneck, Emanuel A1 - Santer, Svetlana A1 - Bekir, Marek T1 - Adsorption of photoresponsive surfactants at solid-liquid interfaces JF - Langmuir N2 - We report on the adsorption kinetics of azoben-zene-containing surfactants on solid surfaces of different hydrophobicity. The understanding of this processes is of great importance for many interfacial phenomena that can be actuated and triggered by light, since the surfactant molecules contain a photoresponsive azobenzene group in their hydrophobic tail. Three surfactant types are studied, differing in the spacer connecting the headgroup and the azobenzene unit by between 6 and 10 CH2 groups. Under irradiation with light of a suitable wavelength, the azobenzene undergoes reversible photoisomerization between two states, a nonpolar trans-state and a highly polar cis-state. Consequently, the surfactant molecule changes its hydrophobicity and thus affinity to a surface depending on the photoisomerization state of the azobenzene. The adsorption behavior on hydrophilic (glass) and hydrophobic (TeflonAF) surfaces is analyzed using quartz crystal microbalance with dissipation (QCM-D) and zeta-potential measurements. At equilibrium, the adsorbed surfactant amount is almost twice as large on glass compared to TeflonAF for both isomers. The adsorption rate for the trans-isomers on both surfaces is similar, but the desorption rate of the trans-isomers is faster at the glass-water interface than at the Teflon-water interface. This result demonstrates that the trans-isomers have higher affinity for the glass surface, so the trans-to-cis ratios on glass and TeflonAF are 80/1 and 2/1, respectively, with similar trends for all three surfactant types. Y1 - 2020 U6 - https://doi.org/10.1021/acs.langmuir.0c02545 SN - 0743-7463 SN - 1520-5827 VL - 36 IS - 46 SP - 14009 EP - 14018 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Silanteva, Irina A. A1 - Komolkin, Andrei A1 - Mamontova, Veronika V. A1 - Gabrusenok, Pavel A1 - Vorontsov-Velyaminov, Pavel N. A1 - Santer, Svetlana A1 - Kasyanenko, Nina A. T1 - Cis-isomers of photosensitive cationic azobenzene surfactants in DNA solutions at different NaCl concentrations BT - Experiment and modeling JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - The DNA interaction with cis-isomers of photosensitive azobenzene-containing surfactants was studied by both experimental methods and computer simulation. It was shown that before the organization of micelles, such surfactants in the cis-conformation form associates of only a single type with a disordered orientation of molecules. In contrast, for trans-isomers, there exist two types of associates with head-to-head or head-to-tail orientations of molecules in dependence on salt concentration in a solution. The comparison of cis- and trans-isomer binding to DNA and the influence of salt concentration on the formation of their complexes with DNA were studied. It was shown that cis-isomers interact with phosphate groups of DNA and that their molecules were also located along the minor groove of DNA. Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpcb.1c07864 SN - 1520-6106 SN - 1520-5207 VL - 125 IS - 40 SP - 11197 EP - 11207 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Niebuur, Bart-Jan A1 - Puchmayr, Jonas A1 - Herold, Christian A1 - Kreuzer, Lucas A1 - Hildebrand, Viet A1 - Müller-Buschbaum, Peter A1 - Laschewsky, Andre A1 - Papadakis, Christine M. T1 - Polysulfobetaines in aqueous solution and in thin film geometry JF - Materials N2 - Polysulfobetaines in aqueous solution show upper critical solution temperature (UCST) behavior. We investigate here the representative of this class of materials, poly (N,N-dimethyl-N-(3-methacrylamidopropyl) ammonio propane sulfonate) (PSPP), with respect to: (i) the dynamics in aqueous solution above the cloud point as function of NaBr concentration; and (ii) the swelling behavior of thin films in water vapor as function of the initial film thickness. For PSPP solutions with a concentration of 5 wt.%, the temperature dependence of the intensity autocorrelation functions is measured with dynamic light scattering as function of molar mass and NaBr concentration (0-8 mM). We found a scaling of behavior for the scattered intensity and dynamic correlation length. The resulting spinodal temperatures showed a maximum at a certain (small) NaBr concentration, which is similar to the behavior of the cloud points measured previously by turbidimetry. The critical exponent of susceptibility depends on NaBr concentration, with a minimum value where the spinodal temperature is maximum and a trend towards the mean-field value of unity with increasing NaBr concentration. In contrast, the critical exponent of the correlation length does not depend on NaBr concentration and is lower than the value of 0.5 predicted by mean-field theory. For PSPP thin films, the swelling behavior was found to depend on film thickness. A film thickness of about 100 nm turns out to be the optimum thickness needed to obtain fast hydration with H2O. KW - polyzwitterions KW - polysulfobetaines KW - dynamic light scattering KW - phase behavior Y1 - 2018 U6 - https://doi.org/10.3390/ma11050850 SN - 1996-1944 VL - 11 IS - 5 PB - MDPI CY - Basel ER - TY - JOUR A1 - Wisotzki, Lutz A1 - Bacon, R. A1 - Brinchmann, J. A1 - Cantalupo, S. A1 - Richter, Philipp A1 - Schaye, J. A1 - Schmidt, Kasper Borello A1 - Urrutia, Tanya A1 - Weilbacher, Peter Michael A1 - Akhlaghi, M. A1 - Bouche, N. A1 - Contini, T. A1 - Guiderdoni, B. A1 - Herenz, E. C. A1 - Inami, H. A1 - Kerutt, Josephine Victoria A1 - Leclercq, F. A1 - Marino, R. A. A1 - Maseda, M. A1 - Monreal-Ibero, A. A1 - Nanayakkara, T. A1 - Richard, J. A1 - Saust, R. A1 - Steinmetz, Matthias A1 - Wendt, Martin T1 - Nearly all the sky is covered by Lyman-alpha emission around high-redshift galaxies JF - Nature : the international weekly journal of science N2 - Galaxies are surrounded by large reservoirs of gas, mostly hydrogen, that are fed by inflows from the intergalactic medium and by outflows from galactic winds. Absorption-line measurements along the lines of sight to bright and rare background quasars indicate that this circumgalactic medium extends far beyond the starlight seen in galaxies, but very little is known about its spatial distribution. The Lyman-alpha transition of atomic hydrogen at a wavelength of 121.6 nanometres is an important tracer of warm (about 104 kelvin) gas in and around galaxies, especially at cosmological redshifts greater than about 1.6 at which the spectral line becomes observable from the ground. Tracing cosmic hydrogen through its Lyman-a emission has been a long-standing goal of observational astrophysics(1-3), but the extremely low surface brightness of the spatially extended emission is a formidable obstacle. A new window into circumgalactic environments was recently opened by the discovery of ubiquitous extended Lyman-alpha emission from hydrogen around high-redshift galaxies(4,5). Such measurements were previously limited to especially favourable systems(6-8) or to the use of massive statistical averaging(9,10) because of the faintness of this emission. Here we report observations of low-surface-brightness Lyman-alpha emission surrounding faint galaxies at redshifts between 3 and 6. We find that the projected sky coverage approaches 100 per cent. The corresponding rate of incidence (the mean number of Lyman-alpha emitters penetrated by any arbitrary line of sight) is well above unity and similar to the incidence rate of high-column-density absorbers frequently detected in the spectra of distant quasars(11-14). This similarity suggests that most circumgalactic atomic hydrogen at these redshifts has now been detected in emission. Y1 - 2018 U6 - https://doi.org/10.1038/s41586-018-0564-6 SN - 0028-0836 SN - 1476-4687 VL - 562 IS - 7726 SP - 229 EP - 232 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Omel'chenko, Oleh A1 - Laing, Carlo R. T1 - Collective states in a ring network of theta neurons JF - Proceedings of the Royal Society of London. Series A, Mathematical, physical and engineering sciences N2 - We consider a ring network of theta neurons with non-local homogeneous coupling. We analyse the corresponding continuum evolution equation, analytically describing all possible steady states and their stability. By considering a number of different parameter sets, we determine the typical bifurcation scenarios of the network, and put on a rigorous footing some previously observed numerical results. KW - theta neurons KW - neural networks KW - bumps Y1 - 2022 U6 - https://doi.org/10.1098/rspa.2021.0817 SN - 1364-5021 SN - 1471-2946 VL - 478 IS - 2259 PB - Royal Society CY - London ER - TY - JOUR A1 - Kosztolowicz, Tadeusz A1 - Metzler, Ralf T1 - Diffusion of antibiotics through a biofilm in the presence of diffusion and absorption barriers JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - We propose a model of antibiotic diffusion through a bacterial biofilm when diffusion and/or absorption barriers develop in the biofilm. The idea of this model is: We deduce details of the diffusion process in a medium in which direct experimental study is difficult, based on probing diffusion in external regions. Since a biofilm has a gel-like consistency, we suppose that subdiffusion of particles in the biofilm may occur. To describe this process we use a fractional subdiffusion-absorption equation with an adjustable anomalous diffusion exponent. The boundary conditions at the boundaries of the biofilm are derived by means of a particle random walk model on a discrete lattice leading to an expression involving a fractional time derivative. We show that the temporal evolution of the total amount of substance that has diffused through the biofilm explicitly depends on whether there is antibiotic absorption in the biofilm. This fact is used to experimentally check for antibiotic absorption in the biofilm and if subdiffusion and absorption parameters of the biofilm change over time. We propose a four-stage model of antibiotic diffusion in biofilm based on the following physical characteristics: whether there is absorption of the antibiotic in the biofilm and whether all biofilm parameters remain unchanged over time. The biological interpretation of the stages, in particular their relation with the bacterial defense mechanisms, is discussed. Theoretical results are compared with empirical results of ciprofloxacin diffusion through Pseudomonas aeruginosa biofilm, and ciprofloxacin and gentamicin diffusion through Proteus mirabilis biofilm. Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevE.102.032408 SN - 2470-0045 SN - 2470-0053 VL - 102 IS - 3 PB - American Physical Society CY - Melville, NY ER - TY - JOUR A1 - Knoche, Lisa A1 - Lisec, Jan A1 - Koch, Matthias T1 - Analysis of electrochemical and liver microsomal transformation products of lasalocid by LC/HRMS JF - Rapid communications in mass spectrometry : RCM N2 - Rationale: Lasalocid (LAS), an ionophore, is used in cattle and poultry farming as feed additive for its antibiotic and growth-promoting properties. Literature on transformation products (TP) resulting from LAS degradation is limited. So far, only hydroxylation is found to occur as the metabolic reaction during the LAS degradation. To investigate potential TPs of LAS, we used electrochemistry (EC) and liver microsome (LM) assays to synthesize TPs, which were identified using liquid chromatography high-resolution mass spectrometry (LC/HRMS). Methods: Electrochemically produced TPs were analyzed online by direct coupling of the electrochemical cell to the electrospray ionization (ESI) source of a Sciex Triple-TOF high resolution mass spectrometer. Then, EC-treated LAS solution was collected and analyzed offline using LC/HRMS to confirm stable TPs and improve their annotation with a chemical structure due to informative MS/MS spectra. In a complementary approach, TPs formed by rat and human microsomal incubation were investigated using LC/HRMS. The resulting data were used to investigate LAS modification reactions and elucidate the chemical structure of obtained TPs. Results: The online measurements identified a broad variety of TPs, resulting from modification reactions like (de-)hydrogenation, hydration, methylation, oxidation as well as adduct formation with methanol. We consistently observed different ion complexations of LAS and LAS-TPs (Na+; 2Na(+) K+; NaNH4+; KNH4+). Two stable methylated EC-TPs were found, structurally annotated, and assigned to a likely modification reaction. Using LM incubation, seven TPs were formed, mostly by oxidation/hydroxylation. After the identification of LM-TPs as Na+-complexes, we identified LM-TPs as K+-complexes. Conclusion: We identified and characterized TPs of LAS using EC- and LM-based methods. Moreover, we found different ion complexes of LAS-based TPs. This knowledge, especially the different ion complexes, may help elucidate the metabolic and environmental degradation pathways of LAS. Y1 - 2022 U6 - https://doi.org/10.1002/rcm.9349 SN - 0951-4198 SN - 1097-0231 VL - 36 IS - 18 PB - Wiley CY - New York, NY ER - TY - JOUR A1 - Hintsche, Marius A1 - Waljor, Veronika A1 - Grossmann, Robert A1 - Kühn, Marco J. A1 - Thormann, Kai M. A1 - Peruani, Fernando A1 - Beta, Carsten T1 - A polar bundle of flagella can drive bacterial swimming by pushing, pulling, or coiling around the cell body JF - Scientific reports N2 - Bacteria swim in sequences of straight runs that are interrupted by turning events. They drive their swimming locomotion with the help of rotating helical flagella. Depending on the number of flagella and their arrangement across the cell body, different run-and-turn patterns can be observed. Here, we present fluorescence microscopy recordings showing that cells of the soil bacterium Pseudomonas putida that are decorated with a polar tuft of helical flagella, can alternate between two distinct swimming patterns. On the one hand, they can undergo a classical push-pull-push cycle that is well known from monopolarly flagellated bacteria but has not been reported for species with a polar bundle of multiple flagella. Alternatively, upon leaving the pulling mode, they can enter a third slow swimming phase, where they propel themselves with their helical bundle wrapped around the cell body. A theoretical estimate based on a random-walk model shows that the spreading of a population of swimmers is strongly enhanced when cycling through a sequence of pushing, pulling, and wrapped flagellar configurations as compared to the simple push-pull-push pattern. Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-16428-9 SN - 2045-2322 VL - 7 PB - Macmillan Publishers Limited, part of Springer Nature CY - London ER - TY - JOUR A1 - Levermann, Anders A1 - Feldmann, Johannes T1 - Scaling of instability timescales of Antarctic outlet glaciers based on one-dimensional similitude analysis JF - The Cryosphere : TC ; an interactive open access journal of the European Geosciences Union N2 - Recent observations and ice-dynamic modeling suggest that a marine ice-sheet instability (MISI) might have been triggered in West Antarctica. The corresponding outlet glaciers, Pine Island Glacier (PIG) and Thwaites Glacier (TG), showed significant retreat during at least the last 2 decades. While other regions in Antarctica have the topographic predisposition for the same kind of instability, it is so far unclear how fast these instabilities would unfold if they were initiated. Here we employ the concept of similitude to estimate the characteristic timescales of several potentially MISI-prone outlet glaciers around the Antarctic coast. Our results suggest that TG and PIG have the fastest response time of all investigated outlets, with TG responding about 1.25 to 2 times as fast as PIG, while other outlets around Antarctica would be up to 10 times slower if destabilized. These results have to be viewed in light of the strong assumptions made in their derivation. These include the absence of ice-shelf buttressing, the one-dimensionality of the approach and the uncertainty of the available data. We argue however that the current topographic situation and the physical conditions of the MISI-prone outlet glaciers carry the information of their respective timescale and that this information can be partially extracted through a similitude analysis. Y1 - 2019 U6 - https://doi.org/10.5194/tc-13-1621-2019 SN - 1994-0416 SN - 1994-0424 VL - 13 IS - 6 SP - 1621 EP - 1633 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - Willner, Sven N. A1 - Otto, Christian A1 - Levermann, Anders T1 - Global economic response to river floods JF - Nature climate change N2 - Increasing Earth’s surface air temperature yields an intensification of its hydrological cycle. As a consequence, the risk of river floods will increase regionally within the next two decades due to the atmospheric warming caused by past anthropogenic greenhouse gas emissions. The direct economic losses caused by these floods can yield regionally heterogeneous losses and gains by propagation within the global trade and supply network. Here we show that, in the absence of large-scale structural adaptation, the total economic losses due to fluvial floods will increase in the next 20 years globally by 17% despite partial compensation through market adjustment within the global trade network. China will suffer the strongest direct losses, with an increase of 82%. The United States is mostly affected indirectly through its trade relations. By contrast to the United States, recent intensification of the trade relations with China leaves the European Union better prepared for the import of production losses in the future. Y1 - 2018 U6 - https://doi.org/10.1038/s41558-018-0173-2 SN - 1758-678X SN - 1758-6798 VL - 8 IS - 7 SP - 594 EP - 598 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Willner, Sven N. A1 - Levermann, Anders A1 - Zhao, Fang A1 - Frieler, Katja T1 - Adaptation required to preserve future high-end river flood risk at present levels JF - Science Advances N2 - Earth’s surface temperature will continue to rise for another 20 to 30 years even with the strongest carbon emission reduction currently considered. The associated changes in rainfall patterns can result in an increased flood risk worldwide. We compute the required increase in flood protection to keep high-end fluvial flood risk at present levels. The analysis is carried out worldwide for subnational administrative units. Most of the United States, Central Europe, and Northeast and West Africa, as well as large parts of India and Indonesia, require the strongest adaptation effort. More than half of the United States needs to at least double their protection within the next two decades. Thus, the need for adaptation to increased river flood is a global problem affecting industrialized regions as much as developing countries. Y1 - 2018 U6 - https://doi.org/10.1126/sciadv.aao1914 SN - 2375-2548 VL - 4 IS - 1 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Wenz, Leonie A1 - Levermann, Anders A1 - Willner, Sven N. A1 - Otto, Christian A1 - Kuhla, Kilian T1 - Post-Brexit no-trade-deal scenario: short-term consumer benefit at the expense of long-term economic development JF - PLoS ONE N2 - After the United Kingdom has left the European Union it remains unclear whether the two parties can successfully negotiate and sign a trade agreement within the transition period. Ongoing negotiations, practical obstacles and resulting uncertainties make it highly unlikely that economic actors would be fully prepared to a “no-trade-deal” situation. Here we provide an economic shock simulation of the immediate aftermath of such a post-Brexit no-trade-deal scenario by computing the time evolution of more than 1.8 million interactions between more than 6,600 economic actors in the global trade network. We find an abrupt decline in the number of goods produced in the UK and the EU. This sudden output reduction is caused by drops in demand as customers on the respective other side of the Channel incorporate the new trade restriction into their decision-making. As a response, producers reduce prices in order to stimulate demand elsewhere. In the short term consumers benefit from lower prices but production value decreases with potentially severe socio-economic consequences in the longer term. KW - model KW - origins KW - chains KW - impact KW - costs Y1 - 2019 VL - 15 IS - 9 PB - PLOS CY - San Francisco ER - TY - JOUR A1 - Kotz, Maximilian A1 - Levermann, Anders A1 - Wenz, Leonie T1 - The effect of rainfall changes on economic production JF - Nature : the international journal of science N2 - Macro-economic assessments of climate impacts lack an analysis of the distribution of daily rainfall, which can resolve both complex societal impact channels and anthropogenically forced changes(1-6). Here, using a global panel of subnational economic output for 1,554 regions worldwide over the past 40 years, we show that economic growth rates are reduced by increases in the number of wet days and in extreme daily rainfall, in addition to responding nonlinearly to the total annual and to the standardized monthly deviations of rainfall. Furthermore, high-income nations and the services and manufacturing sectors are most strongly hindered by both measures of daily rainfall, complementing previous work that emphasized the beneficial effects of additional total annual rainfall in low-income, agriculturally dependent economies(4,7). By assessing the distribution of rainfall at multiple timescales and the effects on different sectors, we uncover channels through which climatic conditions can affect the economy. These results suggest that anthropogenic intensification of daily rainfall extremes(8-10) will have negative global economic consequences that require further assessment by those who wish to evaluate the costs of anthropogenic climate change. Y1 - 2022 U6 - https://doi.org/10.1038/s41586-021-04283-8 SN - 0028-0836 SN - 1476-4687 VL - 601 IS - 7892 SP - 223 EP - 227 PB - Macmillan Publishers Limited, part of Springer Nature CY - London ER - TY - JOUR A1 - Schué, Emmanuelle A1 - Kopyshev, Alexey A1 - Lutz, Jean-François A1 - Börner, Hans G. T1 - Molecular bottle brushes with positioned selenols BT - Extending the toolbox of oxidative single polymer chain folding with conformation analysis by atomic force microscopy JF - Journal of Polymer Science N2 - A synthesis route to controlled and dynamic single polymer chain folding is reported. Sequence-controlled macromolecules containing precisely located selenol moieties within a polymer chain are synthesized. Oxidation of selenol functionalities lead to diselenide bridges and induces controlled intramolecular crosslinking to generate single chain collapse. The cyclization process is successfully characterized by SEC as well as by H-1 NMR and 2D HSQC NMR spectroscopies. In order to gain insight on the molecular level to reveal the degree of structural control, the folded polymers are transformed into folded molecular brushes that are known to be visualizable as single molecule structures by AFM. The "grafting onto" approach is performed by using triazolinedione-diene reaction to graft the side chain polymers. A series of folded molecular brushes as well as the corresponding linear controls are synthesized. AFM visualization is proving the cyclization of the folded backbone by showing globular objects, where non-folded brushes show typical worm-like structures. (C) 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. KW - atomic force microscopy (AFM) KW - diselenide KW - grafted polymers KW - molecular bottle brushes KW - sequence-controlled polymers KW - single chain folding Y1 - 2020 U6 - https://doi.org/10.1002/pola.29496 SN - 2642-4169 VL - 58 IS - 1 SP - 154 EP - 162 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Hempel, Sabrina A1 - Adolphs, Julian A1 - Landwehr, Niels A1 - Willink, Dilya A1 - Janke, David A1 - Amon, Thomas T1 - Supervised machine learning to assess methane emissions of a dairy building with natural ventilation JF - Applied Sciences N2 - A reliable quantification of greenhouse gas emissions is a basis for the development of adequate mitigation measures. Protocols for emission measurements and data analysis approaches to extrapolate to accurate annual emission values are a substantial prerequisite in this context. We systematically analyzed the benefit of supervised machine learning methods to project methane emissions from a naturally ventilated cattle building with a concrete solid floor and manure scraper located in Northern Germany. We took into account approximately 40 weeks of hourly emission measurements and compared model predictions using eight regression approaches, 27 different sampling scenarios and four measures of model accuracy. Data normalization was applied based on median and quartile range. A correlation analysis was performed to evaluate the influence of individual features. This indicated only a very weak linear relation between the methane emission and features that are typically used to predict methane emission values of naturally ventilated barns. It further highlighted the added value of including day-time and squared ambient temperature as features. The error of the predicted emission values was in general below 10%. The results from Gaussian processes, ordinary multilinear regression and neural networks were least robust. More robust results were obtained with multilinear regression with regularization, support vector machines and particularly the ensemble methods gradient boosting and random forest. The latter had the added value to be rather insensitive against the normalization procedure. In the case of multilinear regression, also the removal of not significantly linearly related variables (i.e., keeping only the day-time component) led to robust modeling results. We concluded that measurement protocols with 7 days and six measurement periods can be considered sufficient to model methane emissions from the dairy barn with solid floor with manure scraper, particularly when periods are distributed over the year with a preference for transition periods. Features should be normalized according to median and quartile range and must be carefully selected depending on the modeling approach. KW - greenhouse gas KW - on-farm evaluation KW - emission factor KW - regression KW - ensemble methods KW - gradient boosting KW - random forest KW - neural networks KW - support vector machines Y1 - 2020 U6 - https://doi.org/10.3390/app10196938 SN - 2076-3417 VL - 10 IS - 19 PB - MDPI CY - Basel ER - TY - JOUR A1 - Mayer, Dennis A1 - Picconi, David A1 - Robinson, Matthew S. A1 - Gühr, Markus T1 - Experimental and theoretical gas-phase absorption spectra of thionated uracils JF - Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature N2 - We present a comparative study of the gas-phase UV spectra of uracil and its thionated counterparts (2-thiouracil, 4-thiouracil and 2,4-dithiouracil), closely supported by time-dependent density functional theory calculations to assign the transitions observed. We systematically discuss pure gas-phase spectra for the (thio)uracils in the range of 200-400 nm (similar to 3.2-6.4 eV), and examine the spectra of all four species with a single theoretical approach. We note that specific vibrational modelling is needed to accurately determine the spectra across the examined wavelength range, and systematically model the transitions that appear at wavelengths shorter than 250 nm. Additionally, we find in the cases of 2-thiouracil and 2,4-dithiouracil, that the gas-phase spectra deviate significantly from some previously published solution-phase spectra, especially those collected in basic environments. KW - Thiouracil KW - Uracil KW - UV-VIS Spectroscopy KW - Excited-state calculations; KW - TD-DFT KW - Gas phase Y1 - 2022 U6 - https://doi.org/10.1016/j.chemphys.2022.111500 SN - 0301-0104 VL - 558 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Zhong, Yufei A1 - Causa, Martina A1 - Moore, Gareth John A1 - Krauspe, Philipp A1 - Xiao, Bo A1 - Günther, Florian A1 - Kublitski, Jonas A1 - BarOr, Eyal A1 - Zhou, Erjun A1 - Banerji, Natalie T1 - Sub-picosecond charge-transfer at near-zero driving force in polymer:non-fullerene acceptor blends and bilayers JF - Nature Communications N2 - Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems. Moreover, we establish the influence of the interfacial energetics on the electron and hole transfer rates separately. We demonstrate that charge-transfer timescales remain at a few hundred femtoseconds even at near-zero driving force, which is consistent with the rates predicted by Marcus theory in the normal region, at moderate electronic coupling and at low re-organization energy. Thus, in the design of highly efficient devices, the energy offset at the donor:acceptor interface can be minimized without jeopardizing the charge-transfer rate and without concerns about a current-voltage tradeoff. KW - organic solar cell KW - electron-transfer KW - Donor-Acceptor (DA) interface KW - transfer dynamics KW - donor KW - seperation KW - efficiency KW - impact KW - energy KW - photovoltaics Y1 - 2020 U6 - https://doi.org/10.1038/s41467-020-14549-w SN - 2041-1723 VL - 11 IS - 1 SP - 1 EP - 10 PB - Nature Publishing Group UK CY - London ER - TY - JOUR A1 - Schröder, Jakob A1 - Evans, Alexander A1 - Mishurova, Tatiana A1 - Ulbricht, Alexander A1 - Sprengel, Maximilian A1 - Serrano-Munoz, Itziar A1 - Fritsch, Tobias A1 - Kromm, Arne A1 - Kannengießer, Thomas A1 - Bruno, Giovanni T1 - Diffraction-based residual stress characterization in laser additive manufacturing of metals JF - Metals : open access journal N2 - Laser-based additive manufacturing methods allow the production of complex metal structures within a single manufacturing step. However, the localized heat input and the layer-wise manufacturing manner give rise to large thermal gradients. Therefore, large internal stress (IS) during the process (and consequently residual stress (RS) at the end of production) is generated within the parts. This IS or RS can either lead to distortion or cracking during fabrication or in-service part failure, respectively. With this in view, the knowledge on the magnitude and spatial distribution of RS is important to develop strategies for its mitigation. Specifically, diffraction-based methods allow the spatial resolved determination of RS in a non-destructive fashion. In this review, common diffraction-based methods to determine RS in laser-based additive manufactured parts are presented. In fact, the unique microstructures and textures associated to laser-based additive manufacturing processes pose metrological challenges. Based on the literature review, it is recommended to (a) use mechanically relaxed samples measured in several orientations as appropriate strain-free lattice spacing, instead of powder, (b) consider that an appropriate grain-interaction model to calculate diffraction-elastic constants is both material- and texture-dependent and may differ from the conventionally manufactured variant. Further metrological challenges are critically reviewed and future demands in this research field are discussed. KW - laser-based additive manufacturing KW - residual stress analysis KW - X-ray and KW - neutron diffraction KW - diffraction-elastic constants KW - strain-free lattice KW - spacing Y1 - 2021 U6 - https://doi.org/10.3390/met11111830 SN - 2075-4701 VL - 11 IS - 11 PB - MDPI CY - Basel ER - TY - JOUR A1 - Alirezaeizanjani, Zahra A1 - Großmann, Robert A1 - Pfeifer, Veronika A1 - Hintsche, Marius A1 - Beta, Carsten T1 - Chemotaxis strategies of bacteria with multiple run modes JF - Science advances N2 - Bacterial chemotaxis-a fundamental example of directional navigation in the living world-is key to many biological processes, including the spreading of bacterial infections. Many bacterial species were recently reported to exhibit several distinct swimming modes-the flagella may, for example, push the cell body or wrap around it. How do the different run modes shape the chemotaxis strategy of a multimode swimmer? Here, we investigate chemotactic motion of the soil bacterium Pseudomonas putida as a model organism. By simultaneously tracking the position of the cell body and the configuration of its flagella, we demonstrate that individual run modes show different chemotactic responses in nutrition gradients and, thus, constitute distinct behavioral states. On the basis of an active particle model, we demonstrate that switching between multiple run states that differ in their speed and responsiveness provides the basis for robust and efficient chemotaxis in complex natural habitats. KW - exploit KW - flagellum KW - instability KW - time Y1 - 2020 U6 - https://doi.org/10.1126/sciadv.aaz6153 SN - 2375-2548 VL - 6 IS - 22 PB - American Association for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Weber, Ariane A1 - Bahrs, Marco A1 - Alirezaeizanjani, Zahra A1 - Zhang, Xingyu A1 - Beta, Carsten A1 - Zaburdaev, Vasily T1 - Rectification of Bacterial Diffusion in Microfluidic Labyrinths JF - Frontiers in Physics N2 - In nature as well as in the context of infection and medical applications, bacteria often have to move in highly complex environments such as soil or tissues. Previous studies have shown that bacteria strongly interact with their surroundings and are often guided by confinements. Here, we investigate theoretically how the dispersal of swimming bacteria can be augmented by microfluidic environments and validate our theoretical predictions experimentally. We consider a system of bacteria performing the prototypical run-and-tumble motion inside a labyrinth with square lattice geometry. Narrow channels between the square obstacles limit the possibility of bacteria to reorient during tumbling events to an area where channels cross. Thus, by varying the geometry of the lattice it might be possible to control the dispersal of cells. We present a theoretical model quantifying diffusive spreading of a run-and-tumble random walker in a square lattice. Numerical simulations validate our theoretical predictions for the dependence of the diffusion coefficient on the lattice geometry. We show that bacteria moving in square labyrinths exhibit enhanced dispersal as compared to unconfined cells. Importantly, confinement significantly extends the duration of the phase with strongly non-Gaussian diffusion, when the geometry of channels is imprinted in the density profiles of spreading cells. Finally, in good agreement with our theoretical findings, we observe the predicted behaviors in experiments with E. coli bacteria swimming in a square lattice labyrinth created in amicrofluidic device. Altogether, our comprehensive understanding of bacterial dispersal in a simple two-dimensional labyrinth makes the first step toward the analysis of more complex geometries relevant for real world applications. KW - diffusion KW - rectification KW - random walk KW - bacteria KW - confinement Y1 - 2019 U6 - https://doi.org/10.3389/fphy.2019.00148 SN - 2296-424X SN - 0429-7725 VL - 7 PB - Frontiers Media CY - Lausanne ER - TY - JOUR A1 - Seyrich, Maximilian A1 - Alirezaeizanjani, Zahra A1 - Beta, Carsten A1 - Stark, Holger T1 - Statistical parameter inference of bacterial swimming strategies JF - New journal of physics : the open-access journal for physics N2 - We provide a detailed stochastic description of the swimming motion of an E. coli bacterium in two dimension, where we resolve tumble events in time. For this purpose, we set up two Langevin equations for the orientation angle and speed dynamics. Calculating moments, distribution and autocorrelation functions from both Langevin equations and matching them to the same quantities determined from data recorded in experiments, we infer the swimming parameters of E. coli. They are the tumble rate lambda, the tumble time r(-1), the swimming speed v(0), the strength of speed fluctuations sigma, the relative height of speed jumps eta, the thermal value for the rotational diffusion coefficient D-0, and the enhanced rotational diffusivity during tumbling D-T. Conditioning the observables on the swimming direction relative to the gradient of a chemoattractant, we infer the chemotaxis strategies of E. coli. We confirm the classical strategy of a lower tumble rate for swimming up the gradient but also a smaller mean tumble angle (angle bias). The latter is realized by shorter tumbles as well as a slower diffusive reorientation. We also find that speed fluctuations are increased by about 30% when swimming up the gradient compared to the reversed direction. KW - E.coli KW - run and tumble KW - chemotaxis KW - stochastic processes KW - bacterial swimming strategies KW - parameter inference Y1 - 2018 U6 - https://doi.org/10.1088/1367-2630/aae72c SN - 1367-2630 VL - 20 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Ueckerdt, Falko A1 - Frieler, Katja A1 - Lange, Stefan A1 - Wenz, Leonie A1 - Luderer, Gunnar A1 - Levermann, Anders T1 - The economically optimal warming limit of the planet JF - Earth system dynamics N2 - Both climate-change damages and climate-change mitigation will incur economic costs. While the risk of severe damages increases with the level of global warming (Dell et al., 2014; IPCC, 2014b, 2018; Lenton et al., 2008), mitigating costs increase steeply with more stringent warming limits (IPCC, 2014a; Luderer et al., 2013; Rogelj et al., 2015). Here, we show that the global warming limit that minimizes this century's total economic costs of climate change lies between 1.9 and 2 ∘C, if temperature changes continue to impact national economic growth rates as observed in the past and if instantaneous growth effects are neither compensated nor amplified by additional growth effects in the following years. The result is robust across a wide range of normative assumptions on the valuation of future welfare and inequality aversion. We combine estimates of climate-change impacts on economic growth for 186 countries (applying an empirical damage function from Burke et al., 2015) with mitigation costs derived from a state-of-the-art energy–economy–climate model with a wide range of highly resolved mitigation options (Kriegler et al., 2017; Luderer et al., 2013, 2015). Our purely economic assessment, even though it omits non-market damages, provides support for the international Paris Agreement on climate change. The political goal of limiting global warming to “well below 2 degrees” is thus also an economically optimal goal given above assumptions on adaptation and damage persistence. Y1 - 2019 U6 - https://doi.org/10.5194/esd-10-741-2019 SN - 2190-4979 SN - 2190-4987 VL - 10 IS - 4 SP - 741 EP - 763 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - Feldmann, Johannes A1 - Levermann, Anders A1 - Mengel, Matthias T1 - Stabilizing the West Antarctic Ice Sheet by surface mass deposition JF - Science Advances N2 - There is evidence that a self-sustaining ice discharge from the West Antarctic Ice Sheet (WAIS) has started, potentially leading to its disintegration. The associated sea level rise of more than 3m would pose a serious challenge to highly populated areas including metropolises such as Calcutta, Shanghai, New York City, and Tokyo. Here, we show that the WAIS may be stabilized through mass deposition in coastal regions around Pine Island and Thwaites glaciers. In our numerical simulations, a minimum of 7400 Gt of additional snowfall stabilizes the flow if applied over a short period of 10 years onto the region (-2 mm year(-1) sea level equivalent). Mass deposition at a lower rate increases the intervention time and the required total amount of snow. We find that the precise conditions of such an operation are crucial, and potential benefits need to be weighed against environmental hazards, future risks, and enormous technical challenges. Y1 - 2019 U6 - https://doi.org/10.1126/sciadv.aaw4132 SN - 2375-2548 VL - 5 IS - 7 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Glanemann, Nicole A1 - Willner, Sven N. A1 - Levermann, Anders T1 - Paris Climate Agreement passes the cost-benefit test JF - Nature Communications N2 - The Paris Climate Agreement aims to keep temperature rise well below 2 degrees C. This implies mitigation costs as well as avoided climate damages. Here we show that independent of the normative assumptions of inequality aversion and time preferences, the agreement constitutes the economically optimal policy pathway for the century. To this end we consistently incorporate a damage-cost curve reproducing the observed relation between temperature and economic growth into the integrated assessment model DICE. We thus provide an intertemporally optimizing cost-benefit analysis of this century's climate problem. We account for uncertainties regarding the damage curve, climate sensitivity, socioeconomic future, and mitigation costs. The resulting optimal temperature is robust as can be understood from the generic temperature-dependence of the mitigation costs and the level of damages inferred from the observed temperature-growth relationship. Our results show that the politically motivated Paris Climate Agreement also represents the economically favourable pathway, if carried out properly. Y1 - 2020 U6 - https://doi.org/10.1038/s41467-019-13961-1 SN - 2041-1723 VL - 11 IS - 1 PB - Nature Publishing Group CY - London ER - TY - JOUR A1 - Pasemann, Gregor A1 - Flemming, Sven A1 - Alonso, Sergio A1 - Beta, Carsten A1 - Stannat, Wilhelm T1 - Diffusivity estimation for activator-inhibitor models BT - theory and application to intracellular dynamics of the actin cytoskeleton JF - Journal of nonlinear science N2 - A theory for diffusivity estimation for spatially extended activator-inhibitor dynamics modeling the evolution of intracellular signaling networks is developed in the mathematical framework of stochastic reaction-diffusion systems. In order to account for model uncertainties, we extend the results for parameter estimation for semilinear stochastic partial differential equations, as developed in Pasemann and Stannat (Electron J Stat 14(1):547-579, 2020), to the problem of joint estimation of diffusivity and parametrized reaction terms. Our theoretical findings are applied to the estimation of effective diffusivity of signaling components contributing to intracellular dynamics of the actin cytoskeleton in the model organism Dictyostelium discoideum. KW - Parametric drift estimation KW - Stochastic reaction– diffusion KW - systems KW - Maximum likelihood estimation KW - Actin cytoskeleton dynamics Y1 - 2021 U6 - https://doi.org/10.1007/s00332-021-09714-4 SN - 0938-8974 SN - 1432-1467 VL - 31 IS - 3 PB - Springer CY - New York ER - TY - JOUR A1 - Gengel, Erik A1 - Pikovskij, Arkadij T1 - Phase reconstruction from oscillatory data with iterated Hilbert transform embeddings BT - benefits and limitations JF - Physica : D, Nonlinear phenomena N2 - In the data analysis of oscillatory systems, methods based on phase reconstruction are widely used to characterize phase-locking properties and inferring the phase dynamics. The main component in these studies is an extraction of the phase from a time series of an oscillating scalar observable. We discuss a practical procedure of phase reconstruction by virtue of a recently proposed method termed iterated Hilbert transform embeddings. We exemplify the potential benefits and limitations of the approach by applying it to a generic observable of a forced Stuart-Landau oscillator. Although in many cases, unavoidable amplitude modulation of the observed signal does not allow for perfect phase reconstruction, in cases of strong stability of oscillations and a high frequency of the forcing, iterated Hilbert transform embeddings significantly improve the quality of the reconstructed phase. We also demonstrate that for significant amplitude modulation, iterated embeddings do not provide any improvement. KW - Data analysis KW - Phase reconstruction KW - Hilbert transform Y1 - 2021 U6 - https://doi.org/10.1016/j.physd.2021.133070 SN - 0167-2789 SN - 1872-8022 VL - 429 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Goychuk, Igor A1 - Goychuk, Andriy T1 - Stochastic Wilson BT - Cowan models of neuronal network dynamics with memory and delay JF - New journal of physics N2 - We consider a simple Markovian class of the stochastic Wilson–Cowan type models of neuronal network dynamics, which incorporates stochastic delay caused by the existence of a refractory period of neurons. From the point of view of the dynamics of the individual elements, we are dealing with a network of non-Markovian stochastic two-state oscillators with memory, which are coupled globally in a mean-field fashion. This interrelation of a higher-dimensional Markovian and lower-dimensional non-Markovian dynamics is discussed in its relevance to the general problem of the network dynamics of complex elements possessing memory. The simplest model of this class is provided by a three-state Markovian neuron with one refractory state, which causes firing delay with an exponentially decaying memory within the two-state reduced model. This basic model is used to study critical avalanche dynamics (the noise sustained criticality) in a balanced feedforward network consisting of the excitatory and inhibitory neurons. Such avalanches emerge due to the network size dependent noise (mesoscopic noise). Numerical simulations reveal an intermediate power law in the distribution of avalanche sizes with the critical exponent around −1.16. We show that this power law is robust upon a variation of the refractory time over several orders of magnitude. However, the avalanche time distribution is biexponential. It does not reflect any genuine power law dependence. KW - neuronal networks KW - stochastic models KW - memory and delay KW - critical avalanche dynamics Y1 - 2015 U6 - https://doi.org/10.1088/1367-2630/17/4/045029 SN - 1367-2630 VL - 17 IS - 4 PB - Deutsche Physikalische Gesellschaft, Institute of Physics CY - Bad Honnef, London ER - TY - JOUR A1 - Bauer, Maximilian A1 - Godec, Aljaž A1 - Metzler, Ralf T1 - Diffusion of finite-size particles in two-dimensional channels with random wall configurations JF - Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies N2 - Diffusion of chemicals or tracer molecules through complex systems containing irregularly shaped channels is important in many applications. Most theoretical studies based on the famed Fick–Jacobs equation focus on the idealised case of infinitely small particles and reflecting boundaries. In this study we use numerical simulations to consider the transport of finite-size particles through asymmetrical two-dimensional channels. Additionally, we examine transient binding of the molecules to the channel walls by applying sticky boundary conditions. We consider an ensemble of particles diffusing in independent channels, which are characterised by common structural parameters. We compare our results for the long-time effective diffusion coefficient with a recent theoretical formula obtained by Dagdug and Pineda [J. Chem. Phys., 2012, 137, 024107]. KW - anomalous diffusion KW - fractional dynamics KW - transport KW - nonergodicity KW - coefficient Y1 - 2014 U6 - https://doi.org/10.1039/C3CP55160A SN - 1463-9084 SN - 1463-9076 VL - 16 IS - 13 SP - 6118 EP - 6128 PB - RSC Publications CY - Cambridge ER - TY - JOUR A1 - Pikovskij, Arkadij T1 - Synchronization of oscillators with hyperbolic chaotic phases JF - Izvestija vysšich učebnych zavedenij : naučno-techničeskij žurnal = Izvestiya VUZ. Prikladnaja nelinejnaja dinamika = Applied nonlinear dynamics N2 - Topic and aim. Synchronization in populations of coupled oscillators can be characterized with order parameters that describe collective order in ensembles. A dependence of the order parameter on the coupling constants is well-known for coupled periodic oscillators. The goal of the study is to extend this analysis to ensembles of oscillators with chaotic phases, moreover with phases possessing hyperbolic chaos. Models and methods. Two models are studied in the paper. One is an abstract discrete-time map, composed with a hyperbolic Bernoulli transformation and with Kuramoto dynamics. Another model is a system of coupled continuous-time chaotic oscillators, where each individual oscillator has a hyperbolic attractor of Smale-Williams type. Results. The discrete-time model is studied with the Ott-Antonsen ansatz, which is shown to be invariant under the application of the Bernoulli map. The analysis of the resulting map for the order parameter shows, that the asynchronouis state is always stable, but the synchronous one becomes stable above a certain coupling strength. Numerical analysis of the continuous-time model reveals a complex sequence of transitions from an asynchronous state to a completely synchronous hyperbolic chaos, with intermediate stages that include regimes with periodic in time mean field, as well as with weakly and strongly irregular mean field variations. Discussion. Results demonstrate that synchronization of systems with hyperbolic chaos of phases is possible, although a rather strong coupling is required. The approach can be applied to other systems of interacting units with hyperbolic chaotic dynamics. N2 - Тема и цель. Синхронизация в популяциях связанных осцилляторов может быть охарактеризована параметрами порядка, описывающими коллективный порядок в ансамблях. Зависимость параметра порядка от коэффициентов связи хорошо известна для связанных периодических осцилляторов. Целью данного исследования является обобщение этого анализа на ансамбли осцилляторов с хаотическими фазами, а именно, с фазами, распределёнными на гиперболическом аттракторе. Модели и методы. В работе исследуются две модели. Первая – абстрактное отображение в дискретном времени, составленное из гиперболического преобразования Бернулли и динамики Курамото. Вторая – это система связанных хаотических осцилляторов в непрерывном времени, где каждый отдельный осциллятор имеет гиперболический аттрактор типа Смейла–Вильямса. Результаты. Модель в дискретном времени изучается с помощью подхода Отта–Антонсена, который, как показано, инвариантен при применении отображения Бернулли. Анализ полученного отображения по параметрам порядка показывает, что асинхронное состояние всегда устойчиво, а синхронное состояние становится устойчивым выше определенной силы связи. Численный анализ модели в непрерывном времени показывает сложную последовательность переходов из асинхронного состояния в полностью синхронный гиперболический хаос с промежуточными стадиями, которые включают режимы с периодическим во времени средним полем, а также со слабо и сильно нерегулярными вариациями среднего поля. Обсуждение. Результаты показывают, что синхронизация систем с гиперболическим фазовым хаосом возможна, хотя требуется довольно сильная связь. Данный подход может быть применен и к другим системам взаимодействующих звеньев с гиперболической хаотической динамикой. T2 - Синхронизация осцилляторов с гиперболическими хаотическими фазами KW - hyperbolic attractor KW - synchronization KW - collective dynamics KW - иперболический аттрактор KW - синхронизация KW - оллективная динамика Y1 - 2021 U6 - https://doi.org/10.18500/0869-6632-2021-29-1-78-87 SN - 0869-6632 SN - 2542-1905 VL - 29 IS - 1 SP - 78 EP - 87 PB - Saratov State University CY - Saratov ER - TY - JOUR A1 - Cano Crespo, Ana A1 - Traxl, Dominik A1 - Thonicke, Kirsten T1 - Spatio-temporal patterns of extreme fires in Amazonian forests JF - European physical journal special topics N2 - Fires are a fundamental part of the Earth System. In the last decades, they have been altering ecosystem structure, biogeochemical cycles and atmospheric composition with unprecedented rapidity. In this study, we implement a complex networks-based methodology to track individual fires over space and time. We focus on extreme fires-the 5% most intense fires-in the tropical forests of the Brazilian Legal Amazon over the period 2002-2019. We analyse the interannual variability in the number and spatial patterns of extreme forest fires in years with diverse climatic conditions and anthropogenic pressure to examine potential synergies between climate and anthropogenic drivers. We observe that major droughts, that increase forest flammability, co-occur with high extreme fire years but also that it is fundamental to consider anthropogenic activities to understand the distribution of extreme fires. Deforestation fires, fires escaping from managed lands, and other types of forest degradation and fragmentation provide the ignition sources for fires to ignite in the forests. We find that all extreme forest fires identified are located within a 0.5-km distance from forest edges, and up to 56% of them are within a 1-km distance from roads (which increases to 73% within 5 km), showing a strong correlation that defines spatial patterns of extreme fires. Y1 - 2021 U6 - https://doi.org/10.1140/epjs/s11734-021-00164-3 SN - 1951-6355 SN - 1951-6401 VL - 230 IS - 14-15 SP - 3033 EP - 3044 PB - Springer CY - Berlin ; Heidelberg ER - TY - JOUR A1 - Bolotov, Dmitry A1 - Bolotov, Maxim I. A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovsky, Arkady T1 - Synchronization regimes in an ensemble of phase oscillators coupled through a diffusion field JF - Radiophysics and quantum electronics N2 - We consider an ensemble of identical phase oscillators coupled through a common diffusion field. Using the Ott-Antonsen reduction, we develop dynamical equations for the complex local order parameter and the mean field. The regions of the existence and stability are determined for the totally synchronous, partially synchronous, and asynchronous spatially homogeneous states. A procedure of searching for inhomogeneous states as periodic trajectories of an auxiliary system of the ordinary differential equations is demonstrated. A scenario of emergence of chimera structures from homogeneous synchronous solutions is described. Y1 - 2022 U6 - https://doi.org/10.1007/s11141-022-10173-4 SN - 0033-8443 SN - 1573-9120 VL - 64 IS - 10 SP - 709 EP - 725 PB - Springer CY - New York ER - TY - JOUR A1 - Bolotov, Dmitry A1 - Bolotov, Maxim I. A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Twisted States in a System of Nonlinearly Coupled Phase Oscillators JF - Regular and chaotic dynamics : international scientific journal N2 - We study the dynamics of the ring of identical phase oscillators with nonlinear nonlocal coupling. Using the Ott - Antonsen approach, the problem is formulated as a system of partial derivative equations for the local complex order parameter. In this framework, we investigate the existence and stability of twisted states. Both fully coherent and partially coherent stable twisted states were found (the latter ones for the first time for identical oscillators). We show that twisted states can be stable starting from a certain critical value of the medium length, or on a length segment. The analytical results are confirmed with direct numerical simulations in finite ensembles. KW - twisted state KW - phase oscillators KW - nonlocal coupling KW - Ott - Antonsen reduction KW - stability analysis Y1 - 2019 U6 - https://doi.org/10.1134/S1560354719060091 SN - 1560-3547 SN - 1468-4845 VL - 24 IS - 6 SP - 717 EP - 724 PB - Pleiades publishing inc CY - Moscow ER - TY - JOUR A1 - Grines, Evgeny A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Describing dynamics of driven multistable oscillators with phase transfer curves JF - Chaos : an interdisciplinary journal of nonlinear science N2 - Phase response curve is an important tool in the studies of stable self-sustained oscillations; it describes a phase shift under action of an external perturbation. We consider multistable oscillators with several stable limit cycles. Under a perturbation, transitions from one oscillating mode to another one may occur. We define phase transfer curves to describe the phase shifts at such transitions. This allows for a construction of one-dimensional maps that characterize periodically kicked multistable oscillators. We show that these maps are good approximations of the full dynamics for large periods of forcing. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5037290 SN - 1054-1500 SN - 1089-7682 VL - 28 IS - 10 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Solitary synchronization waves in distributed oscillator populations JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - We demonstrate the existence of solitary waves of synchrony in one-dimensional arrays of oscillator populations with Laplacian coupling. Characterizing each community with its complex order parameter, we obtain lattice equations similar to those of the discrete nonlinear Schrodinger system. Close to full synchrony, we find solitary waves for the order parameter perturbatively, starting from the known phase compactons and kovatons; these solutions are extended numerically to the full domain of possible synchrony levels. For nonidentical oscillators, the existence of dissipative solitons is shown. Y1 - 2018 U6 - https://doi.org/10.1103/PhysRevE.98.062222 SN - 2470-0045 SN - 2470-0053 VL - 98 IS - 6 SP - 062222-1 EP - 062222-7 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Munyaev, Vyacheslav O. A1 - Smirnov, Lev A. A1 - Kostin, Vasily A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Analytical approach to synchronous states of globally coupled noisy rotators JF - New journal of physics : the open-access journal for physics N2 - We study populations of globally coupled noisy rotators (oscillators with inertia) allowing a nonequilibrium transition from a desynchronized state to a synchronous one (with the nonvanishing order parameter). The newly developed analytical approaches resulted in solutions describing the synchronous state with constant order parameter for weakly inertial rotators, including the case of zero inertia, when the model is reduced to the Kuramoto model of coupled noise oscillators. These approaches provide also analytical criteria distinguishing supercritical and subcritical transitions to the desynchronized state and indicate the universality of such transitions in rotator ensembles. All the obtained analytical results are confirmed by the numerical ones, both by direct simulations of the large ensembles and by solution of the associated Fokker-Planck equation. We also propose generalizations of the developed approaches for setups where different rotators parameters (natural frequencies, masses, noise intensities, strengths and phase shifts in coupling) are dispersed. KW - coupled rotators KW - synchronization transition KW - hysteresis KW - Kuramoto KW - model KW - noisy systems Y1 - 2020 U6 - https://doi.org/10.1088/1367-2630/ab6f93 SN - 1367-2630 VL - 22 IS - 2 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Chimera patterns in the Kuramoto-Battogtokh model JF - Journal of physics : A, Mathematical and theoretical N2 - Kuramoto and Battogtokh (2002 Nonlinear Phenom. Complex Syst. 5 380) discovered chimera states represented by stable coexisting synchrony and asynchrony domains in a lattice of coupled oscillators. After a reformulation in terms of a local order parameter, the problem can be reduced to partial differential equations. We find uniformly rotating, spatially periodic chimera patterns as solutions of a reversible ordinary differential equation, and demonstrate a plethora of such states. In the limit of neutral coupling they reduce to analytical solutions in the form of one-and two-point chimera patterns as well as localized chimera solitons. Patterns at weakly attracting coupling are characterized by virtue of a perturbative approach. Stability analysis reveals that only the simplest chimeras with one synchronous region are stable. KW - nonlocal coupled oscillators KW - chimera state KW - coarse-grained order parameter KW - Ott-Antonsen reduction KW - perturbation approach KW - linear stability analysis Y1 - 2017 U6 - https://doi.org/10.1088/1751-8121/aa55f1 SN - 1751-8113 SN - 1751-8121 VL - 50 IS - 8 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Bolotov, Maxim I. A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Simple and complex chimera states in a nonlinearly coupled oscillatory medium JF - Chaos : an interdisciplinary journal of nonlinear science N2 - We consider chimera states in a one-dimensional medium of nonlinear nonlocally coupled phase oscillators. In terms of a local coarse-grained complex order parameter, the problem of finding stationary rotating nonhomogeneous solutions reduces to a third-order ordinary differential equation. This allows finding chimera-type and other inhomogeneous states as periodic orbits of this equation. Stability calculations reveal that only some of these states are stable. We demonstrate that an oscillatory instability leads to a breathing chimera, for which the synchronous domain splits into subdomains with different mean frequencies. Further development of instability leads to turbulent chimeras. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5011678 SN - 1054-1500 SN - 1089-7682 VL - 28 IS - 4 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Munyaev, Vyacheslav A1 - Smirnov, Lev A. A1 - Kostin, Vasily A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Analytical approach to synchronous states of globally coupled noisy rotators JF - New Journal of Physics N2 - We study populations of globally coupled noisy rotators (oscillators with inertia) allowing a nonequilibrium transition from a desynchronized state to a synchronous one (with the nonvanishing order parameter). The newly developed analytical approaches resulted in solutions describing the synchronous state with constant order parameter for weakly inertial rotators, including the case of zero inertia, when the model is reduced to the Kuramoto model of coupled noise oscillators. These approaches provide also analytical criteria distinguishing supercritical and subcritical transitions to the desynchronized state and indicate the universality of such transitions in rotator ensembles. All the obtained analytical results are confirmed by the numerical ones, both by direct simulations of the large ensembles and by solution of the associated Fokker-Planck equation. We also propose generalizations of the developed approaches for setups where different rotators parameters (natural frequencies, masses, noise intensities, strengths and phase shifts in coupling) are dispersed. KW - coupled rotators KW - synchronization transition KW - hysteresis KW - Kuramoto model KW - noisy systems Y1 - 2019 VL - 22 IS - 2 PB - Springer Science CY - New York ER - TY - JOUR A1 - Smirnov, Lev A. A1 - Bolotov, Maxim A1 - Bolotov, Dmitri A1 - Osipov, Grigory V. A1 - Pikovsky, Arkady T1 - Finite-density-induced motility and turbulence of chimera solitons JF - New Journal of Physics N2 - We consider a one-dimensional oscillatory medium with a coupling through a diffusive linear field. In the limit of fast diffusion this setup reduces to the classical Kuramoto–Battogtokh model. We demonstrate that for a finite diffusion stable chimera solitons, namely localized synchronous domain in an infinite asynchronous environment, are possible. The solitons are stable also for finite density of oscillators, but in this case they sway with a nearly constant speed. This finite-density-induced motility disappears in the continuum limit, as the velocity of the solitons is inverse proportional to the density. A long-wave instability of the homogeneous asynchronous state causes soliton turbulence, which appears as a sequence of soliton mergings and creations. As the instability of the asynchronous state becomes stronger, this turbulence develops into a spatio-temporal intermittency. KW - chimera KW - soliton KW - finite-size effects Y1 - 2022 U6 - https://doi.org/10.1088/1367-2630/ac63d9 SN - 1367-2630 VL - 24 PB - IOP CY - London ER - TY - JOUR A1 - Bolotov, Maxim I. A1 - Smirnov, Lev A. A1 - Osipov, Grigory V. A1 - Pikovskij, Arkadij T1 - Breathing chimera in a system of phase oscillators JF - JETP Letters N2 - Chimera states consisting of synchronous and asynchronous domains in a medium of nonlinearly coupled phase oscillators have been considered. Stationary inhomogeneous solutions of the Ott-Antonsen equation for a complex order parameter that correspond to fundamental chimeras have been constructed. The direct numerical simulation has shown that these structures under certain conditions are transformed to oscillatory (breathing) chimera regimes because of the development of instability. Y1 - 2017 U6 - https://doi.org/10.1134/S0021364017180059 SN - 0021-3640 SN - 1090-6487 VL - 106 SP - 393 EP - 399 PB - Pleiades Publ. CY - New York ER - TY - JOUR A1 - Caesar, Levke A1 - Rahmstorf, Stefan A1 - Feulner, Georg T1 - On the relationship between Atlantic meridional overturning circulation slowdown and global surface warming JF - Environmental research letters N2 - According to established understanding, deep-water formation in the North Atlantic and Southern Ocean keeps the deep ocean cold, counter-acting the downward mixing of heat from the warmer surface waters in the bulk of the world ocean. Therefore, periods of strong Atlantic meridional overturning circulation (AMOC) are expected to coincide with cooling of the deep ocean and warming of the surface waters. It has recently been proposed that this relation may have reversed due to global warming, and that during the past decades a strong AMOC coincides with warming of the deep ocean and relative cooling of the surface, by transporting increasingly warmer waters downward. Here we present multiple lines of evidence, including a statistical evaluation of the observed global mean temperature, ocean heat content, and different AMOC proxies, that lead to the opposite conclusion: even during the current ongoing global temperature rise a strong AMOC warms the surface. The observed weakening of the AMOC has therefore delayed global surface warming rather than enhancing it. Social Media Abstract: The overturning circulation in the Atlantic Ocean has weakened in response to global warming, as predicted by climate models. Since it plays an important role in transporting heat, nutrients and carbon, a slowdown will affect global climate processes and the global mean temperature. Scientists have questioned whether this slowdown has worked to cool or warm global surface temperatures. This study analyses the overturning strength and global mean temperature evolution of the past decades and shows that a slowdown acts to reduce the global mean temperature. This is because a slower overturning means less water sinks into the deep ocean in the subpolar North Atlantic. As the surface waters are cold there, the sinking normally cools the deep ocean and thereby indirectly warms the surface, thus less sinking implies less surface warming and has a cooling effect. For the foreseeable future, this means that the slowing of the overturning will likely continue to slightly reduce the effect of the general warming due to increasing greenhouse gas concentrations. KW - Atlantic meridional overturning circulation KW - global surface warming KW - ocean heat uptake Y1 - 2020 U6 - https://doi.org/10.1088/1748-9326/ab63e3 SN - 1748-9326 VL - 15 IS - 2 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Bekir, Marek A1 - Jelken, Joachim A1 - Jung, Se-Hyeong A1 - Pich, Andrij A1 - Pacholski, Claudia A1 - Kopyshev, Alexey A1 - Santer, Svetlana T1 - Dual responsiveness of microgels induced by single light stimulus JF - Applied physics letters N2 - We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented. Y1 - 2021 U6 - https://doi.org/10.1063/5.0036376 SN - 0003-6951 SN - 1077-3118 VL - 118 IS - 9 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Rosenau, Philip A1 - Pikovskij, Arkadij T1 - Waves in strongly nonlinear Gardner-like equations on a lattice JF - Nonlinearity / the Institute of Physics and the London Mathematical Society N2 - We introduce and study a family of lattice equations which may be viewed either as a strongly nonlinear discrete extension of the Gardner equation, or a non-convex variant of the Lotka-Volterra chain. Their deceptively simple form supports a very rich family of complex solitary patterns. Some of these patterns are also found in the quasi-continuum rendition, but the more intriguing ones, like interlaced pairs of solitary waves, or waves which may reverse their direction either spontaneously or due a collision, are an intrinsic feature of the discrete realm. KW - nonlinear lattice KW - solitary wave KW - Gardner equation KW - compacton Y1 - 2021 U6 - https://doi.org/10.1088/1361-6544/ac0f51 SN - 0951-7715 SN - 1361-6544 VL - 34 IS - 8 SP - 5872 EP - 5896 PB - IOP Publ. Ltd. CY - Bristol ER -