TY - JOUR
T1 - Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O
AU - Engin, Selma
AU - González-Vázquez, Jesús
AU - Maliyar, Gianluigi Grimaldi
AU - Milosavljević, Aleksandar R.
AU - Ono, Taishi
AU - Nandi, Saikat
AU - Iablonskyi, Denys
AU - Kooser, Kuno
AU - Bozek, John D.
AU - Decleva, Piero
AU - Kukk, Edwin
AU - Ueda, Kiyoshi
AU - Martín, Fernando
N1 - Funding Information:
We thank Dr. David Ayuso for useful discussions and technical support at the early stages of this research. This work was supported by the MINECO project FIS2016-77889-R and the ERC advanced Grant No. 290853 - XCHEM - within the seventh framework programme of the European Union. We also acknowledge computer time from CCCUAM and Marenostrum Supercomputer Center. Experimental data were obtained at the PLEIADES beamline at the SOLEIL Synchrotron, France (Proposal No. 20151311). F.M. acknowledges support from the "Severo Ochoa" Programme for Centres of Excellence in R&D (MINECO, Grant No. SEV-2016-0686) and the "María de Maeztu" Programme for Units of Excellence in R&D (No. MDM-2014-0377). K.U. acknowledges the support by the Research Program of "Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials" in "Network Joint Research Center for Materials and Devices" and by the TAGEN project. E.K. and K.K. acknowledge financial support from the Academy of Finland.
Funding Information:
We thank Dr. David Ayuso for useful discussions and technical support at the early stages of this research. This work was supported by the MINECO project FIS2016-77889-R and the ERC advanced Grant No. 290853—XCHEM—within the seventh framework programme of the European Union. We also acknowledge computer time from CCC-UAM and Marenostrum Supercomputer Center. Experimental data were obtained at the PLEIADES beamline at the SOLEIL Synchrotron, France (Proposal No. 20151311). F.M. acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant No. SEV-2016-0686) and the “María de Maeztu” Programme for Units of Excellence in R&D (No. MDM-2014-0377). K.U. acknowledges the support by the Research Program of “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in “Network Joint Research Center for Materials and Devices” and by the TAGEN project. E.K. and K.K. acknowledge financial support from the Academy of Finland.
Publisher Copyright:
© 2019 Author(s).
PY - 2019/9/1
Y1 - 2019/9/1
N2 - 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.
AB - 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.
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U2 - 10.1063/1.5106431
DO - 10.1063/1.5106431
M3 - Article
AN - SCOPUS:85069933067
VL - 6
JO - Structural Dynamics
JF - Structural Dynamics
SN - 2329-7778
IS - 5
M1 - 054101
ER -