Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol.
- Vaz da Cruz V Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Ignatova N Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Couto RC Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Fedotov DA Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Rehn DR Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Savchenko V Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Norman P Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Ågren H Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Polyutov S Siberian Federal University, 660041 Krasnoyarsk, Russia.
- Niskanen J Department of Physics and Astronomy, University of Turku, FI-20014 Turun yliopisto, Finland.
- Eckert S Institut für Physik und Astronomie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam, Germany.
- Jay RM Institut für Physik und Astronomie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam, Germany.
- Fondell M Institute for Methods and Instrumentation in Synchrotron Radiation Research G-ISRR, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany.
- Schmitt T Photon Science Division, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland.
- Pietzsch A Institute for Methods and Instrumentation in Synchrotron Radiation Research G-ISRR, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany.
- Föhlisch A Institut für Physik und Astronomie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam, Germany.
- Gel'mukhanov F Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- Odelius M Department of Physics, Stockholm University, AlbaNova University Center, 10691 Stockholm, Sweden.
- Kimberg V Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, 10691 Stockholm, Sweden.
- 2019-06-24
Published in:
- The Journal of chemical physics. - 2019
English
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.
- Language
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- English
- Open access status
- hybrid
- Identifiers
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- DOI 10.1063/1.5092174
- PMID 31228920
- Persistent URL
- https://sonar.ch/global/documents/86431
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