Collective solvent coordinates for the infrared spectrum of HOD in D2O based on an ab initio electrostatic map

被引：140

作者：

Hayashi, T ^{[1
]}

Jansen, TL ^{[1
]}

Zhuang, W ^{[1
]}

Mukamel, S ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2005年 / 109卷 / 01期

关键词：

D O I：

10.1021/jp046685x

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. By combining it with the fluctuating electric field induced by the D2O solvent obtained from molecular dynamics simulations, we calculate the infrared absorption of the O-H stretch. The resulting solvent shift and infrared line shape for three force fields (TIP4P, SPC/E, and SW) are 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. This allows a realistic stochastic Liouville equation simulation of the line shapes which is not restricted to Gaussian frequency fluctuations.

引用

页码：64 / 82

页数：19

共 109 条

[81] Ultrafast vibrational population dynamics of water and related systems: A theoretical perspective [J].