Dynamics of water probed with vibrational echo correlation spectroscopy

John B. Asbury, Tobias Steinel, Kyungwon Kwak, S. A. Corcelli, C. P. Lawrence, J. L. Skinner, M. D. Fayer

Research output: Contribution to journalArticle

299 Citations (Scopus)

Abstract

Vibrational echo correlation spectroscopy experiments on the OD stretch of dilute HOD in H 2O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different infrared pulse bandwidths (pulse durations), making it possible to use data collected from many experiments in which the laser pulse properties are not identical. Accurate measurements of the OD stretch anharmonicity (162 cm -1) are presented and used in the data analysis. In addition, the recent accurate determination of the OD vibrational lifetime (1.45 ps) and the time scale for the production of vibrational relaxation induced broken hydrogen bond "photoproducts" (∼2 ps) aid in the data analysis. The data are analyzed using time dependent diagrammatic perturbation theory to obtain the frequency time correlation function (FTCF). The results are an improved FTCF compared to that obtained previously with vibrational echo correlation spectroscopy. The experimental data and the experimentally determined FTCF are compared to calculations that employ a polarizable water model (SPC-FQ) to calculate the FTCF. The SPC-FQ derived FTCF is much closer to the experimental results than previously tested nonpolarizable water models which are also presented for comparison.

Original languageEnglish
Pages (from-to)12431-12446
Number of pages16
JournalJournal of Chemical Physics
Volume121
Issue number24
DOIs
Publication statusPublished - 2004 Dec 22
Externally publishedYes

ASJC Scopus subject areas

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

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    Asbury, J. B., Steinel, T., Kwak, K., Corcelli, S. A., Lawrence, C. P., Skinner, J. L., & Fayer, M. D. (2004). Dynamics of water probed with vibrational echo correlation spectroscopy. Journal of Chemical Physics, 121(24), 12431-12446. https://doi.org/10.1063/1.1818107