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Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O

Authors :
Selma Engin
Jesús González-Vázquez
Gianluigi Grimaldi Maliyar
Aleksandar R. Milosavljević
Taishi Ono
Saikat Nandi
Denys Iablonskyi
Kuno Kooser
John D. Bozek
Piero Decleva
Edwin Kukk
Kiyoshi Ueda
Fernando Martín
Source :
Structural Dynamics, Vol 6, Iss 5, Pp 054101-054101-10 (2019)
Publication Year :
2019
Publisher :
AIP Publishing LLC and ACA, 2019.

Abstract

We have performed a full-dimensional theoretical study of vibrationally resolved photoelectron emission from the valence shell of the water molecule by using an extension of the static-exchange density functional theory that accounts for ionization as well as for vibrational motion in the symmetric stretching, antisymmetric stretching, and bending modes. At variance with previous studies performed in centrosymmetric molecules, where vibrationally resolved spectra are mostly dominated by the symmetric stretching mode, in the present case, all three modes contribute to the calculated spectra, including intermode couplings. We have found that diffraction of the ejected electron by the various atomic centers is barely visible in the ratios between vibrationally resolved photoelectron spectra corresponding to different vibrational states of the remaining H2O+ cation (the so-called v-ratios), in contrast to the prominent oscillations observed in K-shell ionization of centrosymmetric molecules, including those that only contain hydrogen atoms around the central atoms, e.g., CH4. To validate the conclusions of our work, we have carried out synchrotron radiation experiments at the SOLEIL synchrotron and determined photoelectron spectra and v-ratios for H2O in a wide range of photon energies, from threshold up to 150 eV. The agreement with the theoretical predictions is good.

Subjects

Subjects :
Crystallography
QD901-999

Details

Language :
English
ISSN :
23297778
Volume :
6
Issue :
5
Database :
Directory of Open Access Journals
Journal :
Structural Dynamics
Publication Type :
Academic Journal
Accession number :
edsdoj.47ad3c5d56f44c5a69047d4474a3602
Document Type :
article
Full Text :
https://doi.org/10.1063/1.5106431