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Selective probing of the OH or OD stretch vibration in liquid water using resonant inelastic soft-X-ray scattering

Harada, Yoshihisa ; Tokushima, Takashi LU ; Horikawa, Yuka ; Takahashi, Osamu ; Niwa, Hideharu ; Kobayashi, Masaki ; Oshima, Masaharu ; Senba, Yasunori ; Ohashi, Haruhiko and Wikfeldt, Kjartan Thor , et al. (2013) In Physical Review Letters 111(19).
Abstract

High-resolution O 1s resonant inelastic x-ray scattering spectra of liquid H2O, D2O, and HDO, obtained by excitation near the preedge resonance show, in the elastic line region, well-separated multiple vibrational structures corresponding to the internal OH stretch vibration in the ground state of water. The energy of the first-order vibrational excitation is strongly blueshifted with respect to the main band in the infrared or Raman spectra of water, indicating that water molecules with a highly weakened or broken donating hydrogen bond are correlated with the preedge structure in the x-ray absorption spectrum. The vibrational profile of preedge excited HDO water is well fitted with 50%±20% greater OH-stretch... (More)

High-resolution O 1s resonant inelastic x-ray scattering spectra of liquid H2O, D2O, and HDO, obtained by excitation near the preedge resonance show, in the elastic line region, well-separated multiple vibrational structures corresponding to the internal OH stretch vibration in the ground state of water. The energy of the first-order vibrational excitation is strongly blueshifted with respect to the main band in the infrared or Raman spectra of water, indicating that water molecules with a highly weakened or broken donating hydrogen bond are correlated with the preedge structure in the x-ray absorption spectrum. The vibrational profile of preedge excited HDO water is well fitted with 50%±20% greater OH-stretch contribution compared to OD, which strongly supports a preference for OH being the weakened or broken H-bond in agreement with the well-known picture that D2O makes stronger H-bonds than H2O. Accompanying path-integral molecular dynamics simulations show that this is particularly the case for strongly asymmetrically H-bonded molecules, i.e., those that are selected by preedge excitation.

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publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Review Letters
volume
111
issue
19
article number
193001
publisher
American Physical Society
external identifiers
  • scopus:84887543485
ISSN
0031-9007
DOI
10.1103/PhysRevLett.111.193001
language
English
LU publication?
no
id
17bfecdf-effc-4349-a16c-355e065ee9dd
date added to LUP
2020-05-08 15:08:13
date last changed
2022-04-11 01:53:10
@article{17bfecdf-effc-4349-a16c-355e065ee9dd,
  abstract     = {{<p>High-resolution O 1s resonant inelastic x-ray scattering spectra of liquid H<sub>2</sub>O, D<sub>2</sub>O, and HDO, obtained by excitation near the preedge resonance show, in the elastic line region, well-separated multiple vibrational structures corresponding to the internal OH stretch vibration in the ground state of water. The energy of the first-order vibrational excitation is strongly blueshifted with respect to the main band in the infrared or Raman spectra of water, indicating that water molecules with a highly weakened or broken donating hydrogen bond are correlated with the preedge structure in the x-ray absorption spectrum. The vibrational profile of preedge excited HDO water is well fitted with 50%±20% greater OH-stretch contribution compared to OD, which strongly supports a preference for OH being the weakened or broken H-bond in agreement with the well-known picture that D<sub>2</sub>O makes stronger H-bonds than H<sub>2</sub>O. Accompanying path-integral molecular dynamics simulations show that this is particularly the case for strongly asymmetrically H-bonded molecules, i.e., those that are selected by preedge excitation.</p>}},
  author       = {{Harada, Yoshihisa and Tokushima, Takashi and Horikawa, Yuka and Takahashi, Osamu and Niwa, Hideharu and Kobayashi, Masaki and Oshima, Masaharu and Senba, Yasunori and Ohashi, Haruhiko and Wikfeldt, Kjartan Thor and Nilsson, Anders and Pettersson, Lars G.M. and Shin, Shik}},
  issn         = {{0031-9007}},
  language     = {{eng}},
  month        = {{11}},
  number       = {{19}},
  publisher    = {{American Physical Society}},
  series       = {{Physical Review Letters}},
  title        = {{Selective probing of the OH or OD stretch vibration in liquid water using resonant inelastic soft-X-ray scattering}},
  url          = {{http://dx.doi.org/10.1103/PhysRevLett.111.193001}},
  doi          = {{10.1103/PhysRevLett.111.193001}},
  volume       = {{111}},
  year         = {{2013}},
}