Vibrational relaxation of azide ion in water: The role of intramolecular charge fluctuation and solvent-induced vibrational coupling

Akihiro Morita, Shigeki Kato

Research output: Contribution to journalArticle

113 Citations (Scopus)

Abstract

Vibrational energy relaxation of azide anion in water was investigated with molecular dynamics simulation. The Landau-Teller formula without the solute electronic polarization exceedingly underestimated the relaxation rate of the antisymmetric stretching mode, and thus various relaxation mechanisms were comprehensively evaluated to elucidate the fast relaxation. As a result, the direct relaxation to the vibrational ground state and the intramolecular vibrational redistribution (IVR) to the symmetric stretching mode have equally dominant contributions to the decay rate. Intramolecular charge fluctuation induced by the solute vibrational motion greatly enhanced the friction by the solvent to reproduce the experimental rate fairly well. The isotope effect of H2O and D2O was also elucidated along the present mechanism.

Original languageEnglish
Pages (from-to)5511-5523
Number of pages13
JournalJournal of Chemical Physics
Volume109
Issue number13
DOIs
Publication statusPublished - 1998 Dec 1
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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