论文标题
非线性光谱法的平衡 - 非核环聚合物分子动力学
Equilibrium-nonequilibrium ring-polymer molecular dynamics for nonlinear spectroscopy
论文作者
论文摘要
二维拉曼和杂种terahertz/拉曼光谱技术提供了对凝结相系统的分子结构和动力学的宝贵见解。但是,由于在模拟中纳入量子力学效应的高计算成本,因此很难通过理论来证实实验结果。在这里,我们提出了平衡 - 非核环聚合物分子动力学(RPMD),这是一种实用的计算方法,可以解释核量子对非线性光学光谱的两次响应函数的影响。与最近开发的方法基于双重Kubo转换(DKT)相关函数不同,我们的方法精确地在经典限制中,在经典的极限中,它减少到已建立的均衡含量 - 非苯基经典的经典分子动力学方法。使用基准模型计算,我们证明了平衡 - 非核RPMD的优势比经典和基于DKT的方法的优势。重要的是,其推导基于非平衡RPMD,它消除了识别适当的Kubo转换的相关函数的必要性,并为将实时路径 - 综合技术应用于多维光谱范围铺平了道路。
Two-dimensional Raman and hybrid terahertz/Raman spectroscopic techniques provide invaluable insight into molecular structure and dynamics of condensed-phase systems. However, corroborating experimental results with theory is difficult due to the high computational cost of incorporating quantum-mechanical effects in the simulations. Here, we present the equilibrium-nonequilibrium ring-polymer molecular dynamics (RPMD), a practical computational method that can account for nuclear quantum effects on the two-time response function of nonlinear optical spectroscopy. Unlike a recently developed approach based on the double Kubo transformed (DKT) correlation function, our method is exact in the classical limit, where it reduces to the established equilibrium-nonequilibrium classical molecular dynamics method. Using benchmark model calculations, we demonstrate the advantages of the equilibrium-nonequilibrium RPMD over classical and DKT-based approaches. Importantly, its derivation, which is based on the nonequilibrium RPMD, obviates the need for identifying an appropriate Kubo transformed correlation function and paves the way for applying real-time path-integral techniques to multidimensional spectroscopy.