@article{LiuIgnatovaKimbergetal.2022, author = {Liu, Ji-Cai and Ignatova, Nina and Kimberg, Victor and Krasnov, Pavel and F{\"o}hlisch, Alexander and Simon, Marc and Gel'mukhanov, Faris}, title = {Time-resolved study of recoil-induced rotation by X-ray pump - X-ray probe spectroscopy}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {24}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {11}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d1cp05000a}, pages = {6627 -- 6638}, year = {2022}, abstract = {Modern stationary X-ray spectroscopy is unable to resolve rotational structure. In the present paper, we propose to use time-resolved two color X-ray pump-probe spectroscopy with picosecond resolution for real-time monitoring of the rotational dynamics induced by the recoil effect. The proposed technique consists of two steps. The first short pump X-ray pulse ionizes the valence electron, which transfers angular momentum to the molecule. The second time-delayed short probe X-ray pulse resonantly excites a 1s electron to the created valence hole. Due to the recoil-induced angular momentum the molecule rotates and changes the orientation of transition dipole moment of core-excitation with respect to the transition dipole moment of the valence ionization, which results in a temporal modulation of the probe X-ray absorption as a function of the delay time between the pulses. We developed an accurate theory of the X-ray pump-probe spectroscopy of the recoil-induced rotation and study how the energy of the photoelectron and thermal dephasing affect the structure of the time-dependent X-ray absorption using the CO molecule as a case-study. We also discuss the feasibility of experimental observation of our theoretical findings, opening new perspectives in studies of molecular rotational dynamics.}, language = {en} } @article{BornJohanssonLeitneretal.2022, author = {Born, Artur and Johansson, Fredrik O. L. and Leitner, Torsten and Bidermane, Ieva and Kuehn, Danilo and Martensson, Nils and F{\"o}hlisch, Alexander}, title = {The degree of electron itinerancy and shell closing in the core-ionized state of transition metals probed by Auger-photoelectron coincidence spectroscopy}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {24}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {32}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d2cp02477b}, pages = {19218 -- 19222}, year = {2022}, abstract = {Auger-photoelectron coincidence spectroscopy (APECS) has been used to examine the electron correlation and itinerance effects in transition metals Cu, Ni and Co. It is shown that the LVV Auger, in coincidence with 2p photoelectrons, spectra can be represented using atomic multiplet positions if the 3d-shell is localized (atomic-like) and with a self-convoluted valence band for band-like (itinerant) materials as explained using the Cini-Sawatzky model. For transition metals, the 3d band changes from band-like to localized with increasing atomic number, with the possibility of a mixed behavior. Our result shows that the LVV spectra of Cu can be represented by atomic multiplet calculations, those of Co resemble the self-convolution of the valence band and those of Ni are a mixture of both, consistent with the Cini-Sawatzky model.}, language = {en} } @article{BuechnerdaCruzGroveretal.2022, author = {B{\"u}chner, Robby and da Cruz, Vinicius Vaz and Grover, Nitika and Charisiadis, Asterios and Fondell, Mattis and Haverkamp, Robert and Senge, Mathias O. and F{\"o}hlisch, Alexander}, title = {Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {24}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d1cp05420a}, pages = {7505 -- 7511}, year = {2022}, abstract = {Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct access to the crucial excited molecular states within the unusual relaxation pathway. The efficient intersystem crossing, that is El-Sayed forbidden and not facilitated by a heavy atom is confirmed to be the result of the long singlet excited state lifetime (Q(x) 4.9 ns) and thermal effects. Overall, the interplay of stabilization by conservation of angular momenta and vibronic relaxation drive the de-excitation in these chromophores.}, language = {en} } @article{JohanssonLeitnerBidermaneetal.2022, author = {Johansson, Fredrik O. L. and Leitner, Torsten and Bidermane, Ieva and Born, Artur and F{\"o}hlisch, Alexander and Svensson, Svante and M{\aa}rtensson, Nils and Lindblad, Andreas}, title = {Auger- and photoelectron coincidences of molecular O2 adsorbed on Ag(111)}, series = {Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy}, volume = {256}, journal = {Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy}, publisher = {Elsevier}, address = {New York, NY [u.a.]}, issn = {0368-2048}, doi = {10.1016/j.elspec.2022.147174}, pages = {6}, year = {2022}, abstract = {The oxygen on Ag(111) system has been investigated with Auger electron-photoelectron coincidence spectroscopy (APECS). The coincidence spectra between O 1s core level photoelectrons and O KLL Auger electrons have been studied together with Ag(3)d/AgM4,5NN coincidences. We also describe the electron-electron coincidence spectrometer setup, CoESCA, consisting of two angle resolved time-of-flight spectrometers at a synchrotron light source. Contributions from molecular oxygen and chemisorbed oxygen are assigned using the coincidence data, conclusions are drawn primarily from the O 1s/O KLL data. The data acquisition and treatment procedure are also outlined. The chemisorbed oxygen species observed are relevant for the catalytic ethylene oxidation.}, language = {en} } @article{SorgenfreiGiangrisostomiJayetal.2021, author = {Sorgenfrei, Nomi and Giangrisostomi, Erika and Jay, Raphael Martin and K{\"u}hn, Danilo and Neppl, Stefan and Ovsyannikov, Ruslan and Sezen, Hikmet and Svensson, Svante and F{\"o}hlisch, Alexander}, title = {Photodriven transient picosecond top-layer semiconductor to metal phase-transition in p-doped molybdenum disulfide}, series = {Advanced materials}, volume = {33}, journal = {Advanced materials}, number = {14}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.202006957}, pages = {8}, year = {2021}, abstract = {Visible light is shown to create a transient metallic S-Mo-S surface layer on bulk semiconducting p-doped indirect-bandgap 2H-MoS2. Optically created electron-hole pairs separate in the surface band bending region of the p-doped semiconducting crystal causing a transient accumulation of electrons in the surface region. This triggers a reversible 2H-semiconductor to 1T-metal phase-transition of the surface layer. Electron-phonon coupling of the indirect-bandgap p-doped 2H-MoS2 enables this efficient pathway even at a low density of excited electrons with a distinct optical excitation threshold and saturation behavior. This mechanism needs to be taken into consideration when describing the surface properties of illuminated p-doped 2H-MoS2. In particular, light-induced increased charge mobility and surface activation can cause and enhance the photocatalytic and photoassisted electrochemical hydrogen evolution reaction of water on 2H-MoS2. Generally, it opens up for a way to control not only the surface of p-doped 2H-MoS2 but also related dichalcogenides and layered systems. The findings are based on the sensitivity of time-resolved electron spectroscopy for chemical analysis with photon-energy-tuneable synchrotron radiation.}, language = {en} } @article{EckertVazdaCruzOchmannetal.2021, author = {Eckert, Sebastian and Vaz da Cruz, Vin{\´i}cius and Ochmann, Miguel and Ahnen, Inga von and F{\"o}hlisch, Alexander and Huse, Nils}, title = {Breaking the symmetry of pyrimidine}, series = {The journal of physical chemistry letters}, volume = {12}, journal = {The journal of physical chemistry letters}, number = {35}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.1c01865}, pages = {8637 -- 8643}, year = {2021}, abstract = {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.}, language = {en} } @article{OchmannVazdaCruzEckertetal.2022, author = {Ochmann, Miguel and Vaz da Cruz, Vinicius and Eckert, Sebastian and Huse, Nils and F{\"o}hlisch, Alexander}, title = {R-Group stabilization in methylated formamides observed by resonant inelastic X-ray scattering}, series = {Chemical communications: ChemComm}, volume = {58}, journal = {Chemical communications: ChemComm}, number = {63}, publisher = {The Royal Society of Chemistry}, address = {Cambridge}, issn = {1359-7345}, doi = {10.1039/d2cc00053a}, pages = {8834 -- 8837}, year = {2022}, abstract = {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.}, language = {en} } @article{JayEckertMitzneretal.2020, author = {Jay, Raphael M. and Eckert, Sebastian and Mitzner, Rolf and Fondell, Mattis and F{\"o}hlisch, Alexander}, title = {Quantitative evaluation of transient valence orbital occupations in a 3d transition metal complex as seen from the metal and ligand perspective}, series = {Chemical physics letters}, volume = {754}, journal = {Chemical physics letters}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0009-2614}, doi = {10.1016/j.cplett.2020.137681}, pages = {5}, year = {2020}, abstract = {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.}, language = {en} } @article{VazdaCruzEckertFoehlisch2021, author = {Vaz da Cruz, Vin{\´i}cius and Eckert, Sebastian and F{\"o}hlisch, Alexander}, title = {TD-DFT simulations of K-edge resonant inelastic X-ray scattering within the restricted subspace approximation}, series = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, volume = {23}, journal = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d0cp04726k}, pages = {1835 -- 1848}, year = {2021}, abstract = {A scheme for simulations of resonant inelastic X-ray scattering (RIXS) cross-sections within time-dependent density functional theory (TD-DFT) applying the restricted subspace approximation (RSA) is presented. Therein both occupied core and valence Kohn-Sham orbitals are included in the donor-space, while the accepting virtual orbital space in the linear response TD-DFT equations is restricted to efficiently compute both the valence- and core-excited states of the many electron system. This yields a consistent description of all states contributing to the RIXS scattering process within a single calculation. The introduced orbital truncation allows to automatize the method and facilitates RIXS simulations for systems considerably larger than ones accessible with wave-function based methods. Using the nitrogen K-edge RIXS spectra of 2-thiopyridone and its deprotonated anion as a showcase, the method is benchmarked for different exchange-correlation functionals, the impact of the RSA is evaluated, and the effects of explicit solvation are discussed. Improvements compared to simulations in the frozen orbital approximation are also assessed. The general applicability of the framework is further tested by comparison to experimental data from the literature. The use of TD-DFT core-excited states to the calculation of vibrationally resolved RIXS spectra is also investigated by combining potential energy scans along relevant coordinates with wave packet simulations.}, language = {en} } @article{EckertMascarenhasMitzneretal.2022, author = {Eckert, Sebastian and Mascarenhas, Eric Johnn and Mitzner, Rolf and Jay, Raphael Martin and Pietzsch, Annette and Fondell, Mattis and Vaz da Cruz, Vinicius and F{\"o}hlisch, Alexander}, title = {From the free ligand to the transition metal complex}, series = {Inorganic chemistry}, volume = {61}, journal = {Inorganic chemistry}, number = {27}, publisher = {American Chemical Society}, address = {Washington}, issn = {0020-1669}, doi = {10.1021/acs.inorgchem.2c00789}, pages = {10321 -- 10328}, year = {2022}, abstract = {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.}, language = {en} }