1. Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile
- Author
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T. Käämbre, Simo Huotari, Alexander Föhlisch, Kristjan Kunnus, Annette Pietzsch, Mikko Hakala, Kuno Kooser, Johannes Niskanen, Edwin Kukk, Jaakko Koskelo, Wilson Quevedo, and Department of Physics
- Subjects
Double bond ,116 Chemical sciences ,General Physics and Astronomy ,02 engineering and technology ,Electronic structure ,114 Physical sciences ,01 natural sciences ,Spectral line ,0103 physical sciences ,Physical and Theoretical Chemistry ,010306 general physics ,ta216 ,chemistry.chemical_classification ,Valence (chemistry) ,Chemistry ,Scattering ,Institut für Physik und Astronomie ,021001 nanoscience & nanotechnology ,Triple bond ,Resonant inelastic X-ray scattering ,Chemical bond ,ddc:540 ,Condensed Matter::Strongly Correlated Electrons ,Inhouse research on structure dynamics and function of matter ,Atomic physics ,0210 nano-technology - Abstract
In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS. In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C equivalent to N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C equivalent to NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.
- Published
- 2016