Ma Z, Coker D F
Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
J Chem Phys. 2008 Jun 28;128(24):244108. doi: 10.1063/1.2944270.
This paper reviews the linearized path integral approach for computing time dependent properties of systems that can be approximated using a mixed quantum-classical description. This approach is applied to studying vibrational pure dephasing of ground state molecular iodine in a rare gas matrix. The Feynman-Kleinert optimized harmonic approximation for the full system density operator is used to sample initial conditions for the bath degrees of freedom. This extremely efficient approach is compared to alternative initial condition sampling techniques at low temperatures where classical initial condition sampling yields dephasing rates that are nearly an order of magnitude too slow compared to quantum initial condition sampling and experimental results.
本文回顾了用于计算可采用混合量子 - 经典描述近似的系统随时间变化特性的线性化路径积分方法。该方法被应用于研究稀有气体基质中基态分子碘的振动纯退相。采用费曼 - 克莱因特对全系统密度算符的优化谐波近似来对浴自由度的初始条件进行采样。在低温下，将这种极其高效的方法与其他初始条件采样技术进行比较，此时经典初始条件采样产生的退相速率与量子初始条件采样及实验结果相比慢了近一个数量级。
