TY - JOUR A1 - Fischer, Eric Wolfgang A1 - Anders, Janet A1 - Saalfrank, Peter T1 - Cavity-altered thermal isomerization rates and dynamical resonant localization in vibro-polaritonic chemistry JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - It has been experimentally demonstrated that reaction rates for molecules embedded in microfluidic optical cavities are altered when compared to rates observed under "ordinary" reaction conditions. However, precise mechanisms of how strong coupling of an optical cavity mode to molecular vibrations affects the reactivity and how resonance behavior emerges are still under dispute. In the present work, we approach these mechanistic issues from the perspective of a thermal model reaction, the inversion of ammonia along the umbrella mode, in the presence of a single-cavity mode of varying frequency and coupling strength. A topological analysis of the related cavity Born-Oppenheimer potential energy surface in combination with quantum mechanical and transition state theory rate calculations reveals two quantum effects, leading to decelerated reaction rates in qualitative agreement with experiments: the stiffening of quantized modes perpendicular to the reaction path at the transition state, which reduces the number of thermally accessible reaction channels, and the broadening of the barrier region, which attenuates tunneling. We find these two effects to be very robust in a fluctuating environment, causing statistical variations of potential parameters, such as the barrier height. Furthermore, by solving the time-dependent Schrodinger equation in the vibrational strong coupling regime, we identify a resonance behavior, in qualitative agreement with experimental and earlier theoretical work. The latter manifests as reduced reaction probability when the cavity frequency omega(c) is tuned resonant to a molecular reactant frequency. We find this effect to be based on the dynamical localization of the vibro-polaritonic wavepacket in the reactant well. Y1 - 2022 U6 - https://doi.org/10.1063/5.0076434 SN - 0021-9606 SN - 1089-7690 VL - 156 IS - 15 PB - American Institute of Physics CY - Melville, NY ER - TY - JOUR A1 - Sala, Lorenzo A1 - Kabeshkin, Anton T1 - A priori philosophy of nature in Hegel and German rationalism JF - British journal for the history of philosophy : Bjhp N2 - Hegel's many remarks that seem to imply that philosophy should proceed completely a priori pose a problem for his philosophy of nature since, on this reading, Hegel offers an a priori derivation of empirical results of natural sciences. We show how this perception can be mitigated by interpreting Hegel's remarks as broadly in line with the pre-Kantian rationalist notion of a priori and offer reasons for doing so. We show that, rather than being a peculiarity of Hegel's philosophy, the practice of demonstrating a priori the results of empirical sciences was widespread in the pre-Kantian rationalist tradition. We argue that this practice was intelligible in light of the notion of a priori that was still quite prominent during Hegel's life. This notion of a priori differs from Kant's in that, while the latter's notion concerns propositions, the former concerned only their demonstration. According to it, the same proposition could be demonstrated both a posteriori and a priori. Post-Kantian idealists likewise developed projects of demonstrating specific scientific contents a priori. We then make our discussion more concrete by examining a particular case of an a priori derivation of a natural law, namely the law of fall, by both Leibniz and Hegel. KW - Hegel KW - Philosophy of Nature KW - a priori KW - Wolff KW - Leibniz Y1 - 2022 U6 - https://doi.org/10.1080/09608788.2022.2044753 SN - 0960-8788 SN - 1469-3526 VL - 30 IS - 5 SP - 797 EP - 817 PB - Routledge, Taylor & Francis Group CY - London ER - TY - JOUR A1 - Stone, Kate A1 - Vasishth, Shravan A1 - von der Malsburg, Titus Raban T1 - Does entropy modulate the prediction of German long-distance verb particles? JF - PLOS ONE N2 - In this paper we examine the effect of uncertainty on readers' predictions about meaning. In particular, we were interested in how uncertainty might influence the likelihood of committing to a specific sentence meaning. We conducted two event-related potential (ERP) experiments using particle verbs such as turn down and manipulated uncertainty by constraining the context such that readers could be either highly certain about the identity of a distant verb particle, such as turn the bed [...] down, or less certain due to competing particles, such as turn the music [...] up/down. The study was conducted in German, where verb particles appear clause-finally and may be separated from the verb by a large amount of material. We hypothesised that this separation would encourage readers to predict the particle, and that high certainty would make prediction of a specific particle more likely than lower certainty. If a specific particle was predicted, this would reflect a strong commitment to sentence meaning that should incur a higher processing cost if the prediction is wrong. If a specific particle was less likely to be predicted, commitment should be weaker and the processing cost of a wrong prediction lower. If true, this could suggest that uncertainty discourages predictions via an unacceptable cost-benefit ratio. However, given the clear predictions made by the literature, it was surprisingly unclear whether the uncertainty manipulation affected the two ERP components studied, the N400 and the PNP. Bayes factor analyses showed that evidence for our a priori hypothesised effect sizes was inconclusive, although there was decisive evidence against a priori hypothesised effect sizes larger than 1 mu Vfor the N400 and larger than 3 mu V for the PNP. We attribute the inconclusive finding to the properties of verb-particle dependencies that differ from the verb-noun dependencies in which the N400 and PNP are often studied. Y1 - 2022 U6 - https://doi.org/10.1371/journal.pone.0267813 SN - 1932-6203 VL - 17 IS - 8 PB - PLOS CY - San Francisco, California, US ER - TY - JOUR A1 - Trauth, Martin H. A1 - Marwan, Norbert T1 - Introduction-time series analysis for Earth, climate and life interactions JF - Quaternary science reviews : the international multidisciplinary research and review journal Y1 - 2022 U6 - https://doi.org/10.1016/j.quascirev.2022.107475 SN - 0277-3791 SN - 1873-457X VL - 284 PB - Elsevier CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Zhang, Di A1 - Cao, Kai A1 - Yuan, Xiaoping A1 - Wang, Guocan A1 - van der Beek, Pieter A. T1 - Late Oligocene-early Miocene origin of the First Bend of the Yangtze River explained by thrusting-induced river reorganization JF - Geomorphology N2 - The origin of the First Bend of the Yangtze River is key to understanding the birth of the modern Yangtze River. Despite considerable efforts, the timing and mechanism of formation of the First Bend remain highly debated. Inverse river-profile modeling of three tributaries (Chongjiang, Lima, and Gudu) of the Jinsha River, integrated with regional tectonic and geomorphic interpretations, allows the onset of incision at the First Bend to be constrained to 28-20 Ma. The spatio-temporal coincidence of initial river incision and activity of Yulong Thrust Belt in southeastern Tibet highlights thrusting to be fundamental in reshaping the pre-existing stream network at the First Bend. These results enable us to reinterpret a change in sedimentary environment from a braided river to a swamp-like lake in the Jianchuan Basin south of the First Bend, recording the destruction of the hypothesized southwards-flowing paleo-Jinsha and Shuiluo Rivers at ~36-35 Ma by magmatism. During the late Oligoceneearly Miocene, the paleo-Shuiluo River was diverted to the north by focused rock uplift due to thrusting along the Yulong Thrust Belt, which also led to exhumation of the Jianchuan Basin. Diversion of the paleo-Shuiluo River can be explained by capture from a downstream river in the footwall of the Yulong Thrust Belt. Subsequent rapid headward erosion, that was caused by thrusting-induced drop of local base level, is recorded by upstream younging ages for the onset of incision and led to the formation of the First Bend. The combination of new ages for the onset of incision at 28-20 Ma at the First Bend and younger ages upstream indicates northwards expansion of the Jinsha River at a rate of 62 +/- 18 mm/yr. Our results suggest that the origin of the First Bend was likely triggered by thrusting at 28-20 Ma, after which the Yangtze River formed. KW - Tibetan Plateau KW - Yangtze River KW - river incision KW - inverse modeling Y1 - 2022 U6 - https://doi.org/10.1016/j.geomorph.2022.108303 SN - 0169-555X SN - 1872-695X VL - 411 PB - Elsevier Science CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Bär, Christian A1 - Bandara, Lashi T1 - Boundary value problems for general first-order elliptic differential operators JF - Journal of functional analysis N2 - We study boundary value problems for first-order elliptic differential operators on manifolds with compact boundary. The adapted boundary operator need not be selfadjoint and the boundary condition need not be pseudo-local.We show the equivalence of various characterisations of elliptic boundary conditions and demonstrate how the boundary conditions traditionally considered in the literature fit in our framework. The regularity of the solutions up to the boundary is proven. We show that imposing elliptic boundary conditions yields a Fredholm operator if the manifold is compact. We provide examples which are conveniently treated by our methods. KW - elliptic differential operators of firstorder KW - elliptic boundary KW - conditions KW - boundary regularity KW - Fredholm property KW - H-infinity-functional calculus KW - maximal regularity KW - Rarita-Schwinger KW - operator Y1 - 2022 U6 - https://doi.org/10.1016/j.jfa.2022.109445 SN - 0022-1236 SN - 1096-0783 VL - 282 IS - 12 PB - Elsevier CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Hudson, Paul A1 - Thieken, Annegret T1 - The presence of moral hazard regarding flood insurance and German private businesses JF - Natural hazards : journal of the International Society for the Prevention and Mitigation of Natural Hazards N2 - There is a movement towards the concepts of integrated flood risk management and governance. In these concepts, each stakeholder prone to flooding is tasked with actively limiting flood impacts. Currently, relatively more research has focused upon the adaptation of private households and not on private businesses operating in flood-prone areas. This paper offers an extension of this literature on business-level flood adaptation by exploring the potential presence of moral hazard. The analyses are based on survey data collected in the aftermath of six floods across Germany between 2002 and 2013 to provide a first indication of the presence of moral hazard in private businesses. Moral hazard is where increased insurance coverage results in policyholders preparing less, increasing the risk they face, a counterproductive outcome. We present an initial study of moral hazard occurring through three channels: the performance of emergency measures during a flood, changes in precautionary behavior employed before a given flood occurred, and changes in the intention to employ additional precautionary measures after a flood. We find, much like for private households, no strong indication that moral hazard is present regarding past adaptation. However, there is a potential avenue after 2005 for insurance coverage to lower businesses' intentions to employ more adaptation measures after a flood. This has significant policy relevance such as opportunities for strengthening the link between insurance and risk reduction measures and boosting insurance coverage against flooding in general. KW - Flooding KW - Risk reduction KW - Private businesses KW - Insurance KW - Moral hazard KW - Company Y1 - 2022 U6 - https://doi.org/10.1007/s11069-022-05227-9 SN - 0921-030X SN - 1573-0840 VL - 112 IS - 2 SP - 1295 EP - 1319 PB - Springer CY - Dordrecht [u.a.] ER - TY - JOUR A1 - Reifarth, Martin A1 - Bekir, Marek A1 - Bapolisi, Alain M. A1 - Titov, Evgenii A1 - Nusshardt, Fabian A1 - Nowaczyk, Julius A1 - Grigoriev, Dmitry A1 - Sharma, Anjali A1 - Saalfrank, Peter A1 - Santer, Svetlana A1 - Hartlieb, Matthias A1 - Böker, Alexander T1 - A dual pH- and light-responsive spiropyrane-based surfactant BT - investigations on Its switching behavior and remote control over emulsion stability JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - A cationic surfactant containing a spiropyrane unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyrane (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions. KW - Dual-Responsiveness KW - Manipulation of Emulsion Stability KW - Spiropyrane KW - Surfactant KW - Switchable Surfactants KW - pH-Dependent Photoresponsivity Y1 - 2022 U6 - https://doi.org/10.1002/anie.202114687 SN - 1433-7851 SN - 1521-3773 VL - 61 IS - 21 PB - Wiley-VCH CY - Weinheim 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 - Tönjes, Ralf A1 - Kori, Hiroshi T1 - Phase and frequency linear response theory for hyperbolic chaotic oscillators JF - Chaos : an interdisciplinary journal of nonlinear science N2 - We formulate a linear phase and frequency response theory for hyperbolic flows, which generalizes phase response theory for autonomous limit cycle oscillators to hyperbolic chaotic dynamics. The theory is based on a shadowing conjecture, stating the existence of a perturbed trajectory shadowing every unperturbed trajectory on the system attractor for any small enough perturbation of arbitrary duration and a corresponding unique time isomorphism, which we identify as phase such that phase shifts between the unperturbed trajectory and its perturbed shadow are well defined. The phase sensitivity function is the solution of an adjoint linear equation and can be used to estimate the average change of phase velocity to small time dependent or independent perturbations. These changes in frequency are experimentally accessible, giving a convenient way to define and measure phase response curves for chaotic oscillators. The shadowing trajectory and the phase can be constructed explicitly in the tangent space of an unperturbed trajectory using co-variant Lyapunov vectors. It can also be used to identify the limits of the regime of linear response. Y1 - 2022 U6 - https://doi.org/10.1063/5.0064519 SN - 1054-1500 SN - 1089-7682 VL - 32 IS - 4 PB - AIP Publishing CY - Melville ER -