Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile

  • 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 inIn 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.show moreshow less

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Author details:Johannes Niskanen, Kuno Kooser, Jaakko Koskelo, Tanel Käämbre, Kristjan KunnusORCiD, Annette PietzschORCiD, Wilson Quevedo, Mikko Hakala, Alexander FöhlischORCiDGND, Simo Huotari, Edwin Kukk
URN:urn:nbn:de:kobv:517-opus4-395133
Publication series (Volume number):Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe (331)
Publication type:Postprint
Language:English
Date of first publication:2016/09/09
Publication year:2016
Publishing institution:Universität Potsdam
Release date:2017/04/27
Number of pages:7
Source:Phys. Chem. Chem. Phys. 2016) Nr. 18, S. 26026-26032. - DOI: 10.1039/C6CP03220F
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie
DDC classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer review:Referiert
Publishing method:Open Access
License (English):License LogoCreative Commons - Namensnennung 3.0 Unported
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