Theoretical Studies of Vibrational Energy Relaxation in Condensed Media

迈克尔·赫尔曼获得了理论与计算化学项目的资助，对液体中的振动松弛进行理论研究。他将应用路径积分蒙特卡罗计算机模拟技术来计算简单溶剂中小分子振动居群的弛豫率。他将继续改进在实时离散化路径积分中出现的高振荡积分的调理方法。在项目的初始阶段，只考虑简单溶剂中双原子的低洼振动激发。在从这些系统中获得足够的数值经验后，他将考虑具有高振动激发的双原子和多原子的系统，这些系统需要全路径积分理论。液体振动弛豫的理论研究在化学领域是重要的，因为分子获得和失去振动能量的速率影响它们的化学反应速率、它们的能量输运性质和它们的实验观察光谱。

Michael Herman is supported by a grant from the Theoretical and Computational Chemistry Program to perform theoretical studies on vibrational relaxation in liquids. He will apply path-integral Monte Carlo computer simulation techniques to the calculation of the relaxation rate for vibrational populations of small molecules in simple solvents. He will continue to refine the methodology for conditioning of the highly oscillatory integrands which occur in real time discretized path integrals. In the initial phase of the project only low lying vibrational excitations of diatomics in simple solvents will be considered. After sufficient numerical experience has been gained from these systems, he will consider systems with highly vibrationally excited diatomics and polyatomics for which the full path integral theory is required. %%% Theoretical studies of vibrational relaxation in liquids is important in the field of chemistry because the rate at which molecules gain and lose vibrational energy influences their rates of chemical reaction, their energy transport properties and their experimentally observed spectra.