Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 150, Issue 23, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.5092174
Keywords
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Funding
- Swedish Research Council [VR 2015-04510, 2015-03781, 2015-03956, 2016-03619]
- Knut and Alice Wallenberg Foundation [KAW-2013.0020]
- Carl Tryggers Foundation
- Conselho Nacional de Desenvolvimento Cientifico e Tecnologico [CNPq 234625/2014-7]
- European Research Council under the European Union [669531 EDAX]
- Helmholtz Virtual Institute Dynamic Pathways in Multidimensional Landscapes [VI419]
- Swedish National Infrastructure for Computing [SNIC 2018/3-104, 023/07-18]
- Ministry of Education and Science of the Russian Federation [3.2662.2017]
- Vinnova [2015-03956] Funding Source: Vinnova
- Swedish Research Council [2016-03619, 2015-03781, 2015-04510] Funding Source: Swedish Research Council
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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).
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