Dynamics of water probed with vibrational echo correlation spectroscopy

Vibrational echo correlation spectroscopy expts. on the OD stretch of dil. HOD in H2O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different IR pulse bandwidths (pulse durations), making it possible to use data collected from many expts. 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 anal. In addn., the recent accurate detn. of the OD vibrational lifetime (1.45 ps) and the time scale for the prodn. of vibrational relaxation induced broken hydrogen bond "photoproducts" (∼2 ps) aid in the data anal. 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 exptl. data and the exptl. detd. FTCF are compared to calcns. that employ a polarizable water model (SPC-FQ) to calc. the FTCF. The SPC-FQ derived FTCF is much closer to the exptl. results than previously tested nonpolarizable water models which are also presented for comparison. [on SciFinder(R)]     «

Vibrational echo correlation spectroscopy expts. on the OD stretch of dil. HOD in H2O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different IR pulse bandwidths (pulse durations), making it possible to use data collected from many expts. 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 anal. In addn., the recent acc...     »

Anharmonic molecular vibration (OD stretch OD stretch of dil. HOD in H2O probed with vibrational echo correlation spectroscopy) Stretching vibration (OD dynamics of water probed with vibrational echo correlation spectroscopy) Hydrogen bond (breaking dynamics of water probed with vibrational echo correlation spectroscopy) Vibrational relaxation (dynamics of water probed with vibrational echo correlation spectroscopy) Time correlation function (frequency OD stretch of dil. HOD in H2O probed with vibrational echo correlation spectroscopy) Excited vibrational state (lifetime dynamics of water probed with vibrational echo correlation spectroscopy) IR spectra (mid-IR, transient absorption OD stretch of dil. HOD in H2O probed with vibrational echo correlation spectroscopy) Optical absorption (transient OD stretch of dil. HOD in H2O probed with vibrational echo correlation spectroscopy) Photon echo (vibrational dynamics of water probed with vibrational echo correlation spectroscopy) dynamics water vibrational echo correlation hydroxyl stretch anharmonicity     «

Anharmonic molecular vibration (OD stretch OD stretch of dil. HOD in H2O probed with vibrational echo correlation spectroscopy) Stretching vibration (OD dynamics of water probed with vibrational echo correlation spectroscopy) Hydrogen bond (breaking dynamics of water probed with vibrational echo correlation spectroscopy) Vibrational relaxation (dynamics of water probed with vibrational echo correlation spectroscopy) Time correlation function (frequency OD stretch of dil. HOD in H2O probed with v...     »