Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol
| Autor: | Raphael M. Jay, Victor Kimberg, Annette Pietzsch, Michael Odelius, Alexander Föhlisch, Sebastian Eckert, Thorsten Schmitt, Hans Ågren, Daniil A Fedotov, Dirk R. Rehn, Sergey Polyutov, Viktoriia Savchenko, Faris Gel'mukhanov, Mattis Fondell, Johannes Niskanen, Vinícius Vaz da Cruz, Rafael C. Couto, Nina Ignatova, Patrick Norman |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Materials science
Absorption spectroscopy Atom and Molecular Physics and Optics Analytical chemistry General Physics and Astronomy 010402 general chemistry 01 natural sciences Physical Chemistry Spectral line chemistry.chemical_compound 0103 physical sciences Teoretisk kemi Theoretical chemistry core excitation spectra of gas and liquid methanol X ray absorption spectroscopy XAS resonant inelastic X Ray scattering RIXS Franck Condon amplitudes valence excited states ddc:530 Physical and Theoretical Chemistry Absorption (electromagnetic radiation) Theoretical Chemistry Astrophysics::Galaxy Astrophysics Fysikalisk kemi X-ray absorption spectroscopy 010304 chemical physics X-ray Institut für Physik und Astronomie 0104 chemical sciences Resonant inelastic X-ray scattering chemistry Condensed Matter::Strongly Correlated Electrons Atom- och molekylfysik och optik Methanol |
| Zdroj: | The Journal of Chemical Physics |
| Popis: | 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 amp; 8243; 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 amp; 8243; 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 |
| Databáze: | OpenAIRE |
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