DESCRIPTION: An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. Combining with molecular dynamics simulations, it reproduces infrared absorption of the O-H stretch in good agreement with the experiment. A collective coordinate response for the solvent effect is constructed by identifying the main electrostatic field and gradient components contributing to the line shape. The effects of hydrogen-bond forming and breaking kinetics on the linear and coherent third-order infrared spectra of the OH stretch of HOD in D2O are described by Markovian fluctuations and simulated using the stochastic Liouville equations. The asymmetry of the photon-echo spectra larger linewidth on the blue side than on the red side predicted by the FSJ is in better agreement with recent experiments.
REFERENCE:
T. Hayashi, T. Jansen, W. Zhuang, S. Mukamel, "Collective Solvent Coordinates for the Infrared Spectrum of HOD in D2O Based on an Ab Initio Electrostatic Map," J. Phys. Chem. B, 2005, 109, 64-82.
T.
Jansen, T. Hayashi, W Zhuang and S. Mukamel
ˇ°Stochastic Liouville Equations for Hydrogen-Bonding Fluctuations
and Their Signatures in Two-Dimensional Vibrational Spectroscopy of Waterˇ±
J. Chem. Phys. 2005, 123, 114504-114511.