A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile
Tekijät: Niskanen J, Kooser K, Koskelo J, Kaambre T, Kunnus K, Pietzsch A, Quevedo W, Hakala M, Fohlisch A, Huotari S, Kukk E
Kustantaja: ROYAL SOC CHEMISTRY
Julkaisuvuosi: 2016
Journal: Physical Chemistry Chemical Physics
Tietokannassa oleva lehden nimi: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Lehden akronyymi: PHYS CHEM CHEM PHYS
Vuosikerta: 18
Numero: 37
Aloitussivu: 26026
Lopetussivu: 26032
Sivujen määrä: 7
ISSN: 1463-9076
DOI: https://doi.org/10.1039/c6cp03220f
Tiivistelmä
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.
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.
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