Nuclear Quantum Effect on the χ(2) Band Shape of Vibrational Sum Frequency Generation Spectra of Normal and Deuterated Water Surfaces

Tatsuya Ishiyama, Akihiro Morita

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

In the vibrational sum frequency generation (VSFG) spectrum of the air/water interface, there is an open question whether the imaginary spectrum of nonlinear susceptibility Im[χ(2)] has a positive band in the low-frequency tail of the OH stretching band. We previously elucidated by molecular dynamics (MD) analysis of the VSFG spectrum that the positive band could arise from particularly strong hydrogen-bonded water pairs at the water surface. This mechanism should be emphasized in OD stretching in comparison to OH, because OD forms stronger hydrogen bonds. Therefore, we calculated the Im[χ(2)] spectra of normal and deuterated water surfaces by MD simulation including the nuclear quantum effect and demonstrated that the low-frequency positive feature could arise in the tail of the OD stretching band. This positive feature is sensitive to the oxygen-oxygen distance of hydrogen-bonding pairs at the surface and hence the temperature and disappears with increasing temperature.

Original languageEnglish
Pages (from-to)5070-5075
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume10
Issue number17
DOIs
Publication statusPublished - 2019 Sep 5

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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