Toutounji Mohamad
College of Science, Department of Chemistry, P.O. Box 17551, United Arab Emirates University, Al-Ain, United Arab Emirates.
J Chem Phys. 2006 Nov 21;125(19):194520. doi: 10.1063/1.2382916.
Mixed quantum-classical statistical mechanics is employed to calculate dipole moment correlation function and linear absorption spectra. A quantum two-level subsystem interacting with quantum vibrations (primary oscillators) which in turn are coupled to a classical bath composed of infinite set of harmonic oscillators is used as a dissipative system. Starting with mixed quantum-classical Liouville equation for the evaluation of the mixed quantum-classical dipole moment correlation function and using coherent states and the inverse of Baker-Campbell-Hausdorf formula to evaluate the trace over the primary oscillators, whereby, a closed analytical expression for the electronic dipole moment correlation function is obtained. Illustrations of several absorption spectra at different temperatures are provided. An approximate optical four-point correlation is obtained in the high temperature limit. A strategy for deriving an exact optical four-point correlation is suggested.
采用混合量子 - 经典统计力学来计算偶极矩相关函数和线性吸收光谱。一个与量子振动（主振子）相互作用的量子二能级子系统，而这些量子振动又与由无限组简谐振子组成的经典浴耦合，被用作耗散系统。从用于评估混合量子 - 经典偶极矩相关函数的混合量子 - 经典刘维尔方程出发，并使用相干态和贝克 - 坎贝尔 - 豪斯多夫公式的逆来计算主振子上的迹，从而得到电子偶极矩相关函数的封闭解析表达式。给出了不同温度下几个吸收光谱的示例。在高温极限下得到了一个近似的光学四点关联。提出了一种推导精确光学四点关联的策略。
