Vinícius Vaz da Cruz, Nina Ignatova, Rafael Couto, Daniil Fedotov, Dirk R. Rehn, Viktoriia Savchenko, Patrick Norman, Hans Ågren, Sergey Polyutov, Johannes Niskanen, Sebastian Eckert, Raphael Martin Jay, Mattis Fondell, Thorsten Schmitt, Annette Pietzsch, Alexander Föhlisch, Michael Odelius, Victor Kimberg, Faris Gel’mukhanov
- 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 theWe 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).…
MetadatenAuthor details: | Vinícius Vaz da CruzORCiD, Nina IgnatovaORCiD, Rafael CoutoORCiD, Daniil FedotovORCiD, Dirk R. RehnORCiDGND, Viktoriia SavchenkoORCiD, Patrick NormanORCiDGND, Hans Ågren, Sergey PolyutovORCiD, Johannes Niskanen, Sebastian EckertORCiDGND, Raphael Martin JayORCiDGND, Mattis FondellORCiD, Thorsten Schmitt, Annette PietzschORCiD, Alexander FöhlischORCiDGND, Michael OdeliusORCiD, Victor KimbergORCiD, Faris Gel’mukhanov |
---|
DOI: | https://doi.org/10.1063/1.5092174 |
---|
ISSN: | 0021-9606 |
---|
ISSN: | 1089-7690 |
---|
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/31228920 |
---|
Title of parent work (English): | The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr |
---|
Publisher: | American Institute of Physics |
---|
Place of publishing: | Melville |
---|
Publication type: | Article |
---|
Language: | English |
---|
Date of first publication: | 2019/06/17 |
---|
Publication year: | 2019 |
---|
Release date: | 2021/01/21 |
---|
Volume: | 150 |
---|
Issue: | 23 |
---|
Number of pages: | 20 |
---|
Funding institution: | Swedish Research CouncilSwedish Research Council [VR 2015-04510, 2015-03781, 2015-03956, 2016-03619]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW-2013.0020]; Carl Tryggers Foundation; Conselho Nacional de Desenvolvimento Cientifico e TecnologicoNational Council for Scientific and Technological Development (CNPq) [CNPq 234625/2014-7]; European Research Council under the European UnionEuropean Research Council (ERC) [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 FederationMinistry of Education and Science, Russian Federation [3.2662.2017] |
---|
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
---|
DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
---|
Peer review: | Referiert |
---|
Publishing method: | Open Access / Hybrid Open-Access |
---|
License (German): | CC-BY - Namensnennung 4.0 International |
---|