TY - JOUR A1 - Wilkin, Kyle J. A1 - Parrish, Robert M. A1 - Yang, Jie A1 - Wolf, Thomas J. A. A1 - Nunes, J. Pedro F. A1 - Gühr, Markus A1 - Li, Renkai A1 - Shen, Xiaozhe A1 - Zheng, Qiang A1 - Wang, Xijie A1 - Martinez, Todd J. A1 - Centurion, Martin T1 - Diffractive imaging of dissociation and ground-state dynamics in a complex molecule JF - Physical review : A, Atomic, molecular, and optical physics N2 - We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C2F4I2) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p perpendicular to orbital to a mixed 5p parallel to sigma hole and CF2 center dot antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs. Y1 - 2019 U6 - https://doi.org/10.1103/PhysRevA.100.023402 SN - 2469-9926 SN - 2469-9934 VL - 100 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Wolf, Thomas J. A. A1 - Parrish, Robert M. A1 - Myhre, Rolf H. A1 - Martinez, Todd J. A1 - Koch, Henrik A1 - Gühr, Markus T1 - Observation of Ultrafast Intersystem Crossing in Thymine by Extreme Ultraviolet Time-Resolved Photoelectron Spectroscopy JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - We studied the photoinduced ultrafast relaxation dynamics of the nucleobase thymine using gas-phase time-resolved photoelectron spectroscopy. By employing extreme ultraviolet pulses from high harmonic generation for photoionization, we substantially extend our spectral observation window with respect to previous studies. This enables us to follow relaxation of the excited state population all the way to low-lying electronic states including the ground state. In thymine, we observe relaxation from the optically bright (1)pi pi* state of thymine to a dark (1)n pi* state within 80 +/- 30 fs. The (1)n pi* state relaxes further within 3.5 +/- 0.3 ps to a low-lying electronic state. By comparison with quantum chemical simulations, we can unambiguously assign its spectroscopic signature to the (3)pi pi* state. Hence, our study draws a comprehensive picture of the relaxation mechanism of thymine including ultrafast intersystem crossing to the triplet manifold. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpca.9b05573 SN - 1089-5639 SN - 1520-5215 VL - 123 IS - 32 SP - 6897 EP - 6903 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Battistoni, A. A1 - Dürr, H. A. A1 - Gühr, Markus A1 - Wolf, Thomas J. A. T1 - A tilted pulse-front setup for femtosecond transient grating spectroscopy in highly non-collinear geometries JF - Journal of optics N2 - We demonstrate a tilted pulse-front transient grating (TG) technique that allows to optimally utilize time resolution as well as TG line density while probing under grazing incidence as typically done in extreme ultraviolet (EUV) or soft x-ray (SXR) experiments. Our optical setup adapts the pulse front tilt of the two pulses that create the TG to the grazing incident pulse. We demonstrate the technique using all 800 nm femtosecond laser pulses for TG generation on a vanadium dioxide film. We probe that grating via diffraction of a third 800 nm pulse. The time resolution of 90 fs is an improvement by a factor of 30 compared to our previous experiments on the same system. The scheme paves the way for EUV and SXR probing of optically induced TGs on any material. KW - transient grating spectroscopy KW - ultrafast spectroscopy KW - pulse front matching Y1 - 2018 U6 - https://doi.org/10.1088/2040-8986/aad60a SN - 2040-8978 SN - 2040-8986 VL - 20 IS - 9 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Yang, Jie A1 - Zhu, Xiaolei A1 - Wolf, Thomas J. A. A1 - Li, Zheng A1 - Nunes, João Pedro Figueira A1 - Coffee, Ryan A1 - Cryan, James P. A1 - Gühr, Markus A1 - Hegazy, Kareem A1 - Heinz, Tony F. A1 - Jobe, Keith A1 - Li, Renkai A1 - Shen, Xiaozhe A1 - Veccione, Theodore A1 - Weathersby, Stephen A1 - Wilkin, Kyle J. A1 - Yoneda, Charles A1 - Zheng, Qiang A1 - Martinez, Todd J. A1 - Centurion, Martin A1 - Wang, Xijie T1 - Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction JF - Science N2 - Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations. Y1 - 2018 U6 - https://doi.org/10.1126/science.aat0049 SN - 0036-8075 SN - 1095-9203 VL - 361 IS - 6397 SP - 64 EP - 67 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Xiong, Hui A1 - Fang, Li A1 - Osipov, Timur A1 - Kling, Nora G. A1 - Wolf, Thomas J. A. A1 - Sistrunk, Emily A1 - Obaid, Razib A1 - Gühr, Markus A1 - Berrah, Nora T1 - Fragmentation of endohedral fullerene Ho3N@C-80 in an intense femtosecond near-infrared laser field JF - Physical review : A, Atomic, molecular, and optical physics N2 - The fragmentation of gas phase endohedral fullerene, Ho3N@C-80, was investigated using femtosecond near-infrared laser pulses with an ion velocity map imaging spectrometer. We observed that Ho+ abundance associated with carbon cage opening dominates at an intensity of 1.1 x 10(14) W/cm(2). As the intensity increases, the Ho+ yield associated with multifragmentation of the carbon cage exceeds the prominence of Ho+ associated with the gentler carbon cage opening. Moreover, the power law dependence of Ho+ on laser intensity indicates that the transition of the most likely fragmentation mechanisms occurs around 2.0 x 10(14) W/cm(2). Y1 - 2018 U6 - https://doi.org/10.1103/PhysRevA.97.023419 SN - 2469-9926 SN - 2469-9934 VL - 97 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Myhre, Rolf H. A1 - Wolf, Thomas J. A. A1 - Cheng, Lan A1 - Nandi, Saikat A1 - Coriani, Sonia A1 - Gühr, Markus A1 - Koch, Henrik T1 - A theoretical and experimental benchmark study of core-excited states in nitrogen JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. The computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5011148 SN - 0021-9606 SN - 1089-7690 VL - 148 IS - 6 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Xiong, Hui A1 - Mignolet, Benoit A1 - Fang, Li A1 - Osipov, Timur A1 - Wolf, Thomas J. A. A1 - Sistrunk, Emily A1 - Gühr, Markus A1 - Remacle, Francoise A1 - Berrah, Nora T1 - The Role of Super-Atom Molecular Orbitals in Doped Fullerenes in a Femtosecond Intense Laser Field JF - Scientific reports N2 - The interaction of gas phase endohedral fullerene Ho3N@C-80 with intense (0.1-5 x 10(14) W/cm(2)), short (30 fs), 800 nm laser pulses was investigated. The power law dependence of Ho3N@C-80(q+), q = 1-2, was found to be different from that of C-60. Time-dependent density functional theory computations revealed different light-induced ionization mechanisms. Unlike in C-60, in doped fullerenes, the breaking of the cage spherical symmetry makes super atomic molecular orbital (SAMO) states optically active. Theoretical calculations suggest that the fast ionization of the SAMO states in Ho3N@C-80 is responsible for the n = 3 power law for singly charged parent molecules at intensities lower than 1.2 x 10(14) W/cm(2). Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-00124-9 SN - 2045-2322 VL - 7 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Holzmeier, Fabian A1 - Wolf, Thomas J. A. A1 - Gienger, Christian A1 - Wagner, Isabella A1 - Bozek, J. A1 - Nandi, S. A1 - Nicolas, C. A1 - Fischer, Ingo A1 - Gühr, Markus A1 - Fink, Reinhold F. T1 - Normal and resonant Auger spectroscopy of isocyanic acid, HNCO JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - In this paper, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO2 molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a′ resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between −8 and −9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approaches in the computation of core electron spectra. Y1 - 2018 U6 - https://doi.org/10.1063/1.5030621 SN - 0021-9606 SN - 1089-7690 VL - 149 IS - 3 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Wolf, Thomas J. A. A1 - Holzmeier, Fabian A1 - Wagner, Isabella A1 - Berrah, Nora A1 - Bostedt, Christoph A1 - Bozek, John A1 - Bucksbaum, Philip H. A1 - Coffee, Ryan A1 - Cryan, James A1 - Farrell, Joe A1 - Feifel, Raimund A1 - Martinez, Todd J. A1 - McFarland, Brian A1 - Mucke, Melanie A1 - Nandi, Saikat A1 - Tarantelli, Francesco A1 - Fischer, Ingo A1 - Gühr, Markus T1 - Observing Femtosecond Fragmentation Using Ultrafast X-ray-Induced Auger Spectra JF - Applied Sciences N2 - Molecules often fragment after photoionization in the gas phase. Usually, this process can only be investigated spectroscopically as long as there exists electron correlation between the photofragments. Important parameters, like their kinetic energy after separation, cannot be investigated. We are reporting on a femtosecond time-resolved Auger electron spectroscopy study concerning the photofragmentation dynamics of thymine. We observe the appearance of clearly distinguishable signatures from thymine′s neutral photofragment isocyanic acid. Furthermore, we observe a time-dependent shift of its spectrum, which we can attribute to the influence of the charged fragment on the Auger electron. This allows us to map our time-dependent dataset onto the fragmentation coordinate. The time dependence of the shift supports efficient transformation of the excess energy gained from photoionization into kinetic energy of the fragments. Our method is broadly applicable to the investigation of photofragmentation processes. KW - ultrafast dynamics KW - Auger electron spectroscopy KW - photofragmentation KW - photochemistry Y1 - 2017 U6 - https://doi.org/10.3390/app7070681 SN - 2076-3417 VL - 7 IS - 7 PB - MDPI CY - Basel ER - TY - JOUR A1 - Lever, Fabiano A1 - Mayer, Dennis A1 - Metje, Jan A1 - Alisauskas, Skirmantas A1 - Calegari, Francesca A1 - Düsterer, Stefan A1 - Feifel, Raimund A1 - Niebuhr, Mario A1 - Manschwetus, Bastian A1 - Kuhlmann, Marion A1 - Mazza, Tommaso A1 - Robinson, Matthew Scott A1 - Squibb, Richard J. A1 - Trabattoni, Andrea A1 - Wallner, Måns A1 - Wolf, Thomas J. A. A1 - Gühr, Markus T1 - Core-level spectroscopy of 2-thiouracil at the sulfur L1 and L2,3 edges utilizing a SASE free-electron-laser JF - Molecules N2 - In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster–Kronig and Auger–Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy. KW - X-ray KW - photoelectron KW - sulfur KW - thiouracil KW - nucleobases KW - Coster–Kronig KW - Auger–Meitner KW - NEXAFS KW - FLASH Y1 - 2021 SN - 1420-3049 VL - 26 IS - 21 PB - MDPI CY - Basel ER - TY - JOUR A1 - Mayer, Dennis A1 - Lever, Fabiano A1 - Picconi, David A1 - Metje, Jan A1 - Ališauskas, Skirmantas A1 - Calegari, Francesca A1 - Düsterer, Stefan A1 - Ehlert, Christopher A1 - Feifel, Raimund A1 - Niebuhr, Mario A1 - Manschwetus, Bastian A1 - Kuhlmann, Marion A1 - Mazza, Tommaso A1 - Robinson, Matthew Scott A1 - Squibb, Richard James A1 - Trabattoni, Andrea A1 - Wallner, Måns A1 - Saalfrank, Peter A1 - Wolf, Thomas J. A. A1 - Gühr, Markus T1 - Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy JF - Nature Communications N2 - The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-021-27908-y SN - 2041-1723 N1 - These authors contributed equally: D. Mayer, F. Lever. A Publisher Correction to this article was published on 09 March 2022. This article has been updated. VL - 13 PB - Springer Nature CY - Berlin ER -