Department of Theoretical Physics, Faculty of Physics, Vilnius University, Sauletekio 9-III, 10222 Vilnius, Lithuania.
J Chem Phys. 2017 Aug 21;147(7):074114. doi: 10.1063/1.4985910.
A straightforward extension to the stochastic time-dependent variational approach allows the introduction of higher-order interaction effects to the Hamiltonian of an electronic-vibrational system. This is done using an Ansatz for the global wavefunction, describing vibrational wavepackets as squeezed coherent states (a generalized version of Davydov Ansatz). The approach allows quantum dynamics simulation and simulation of spectroscopic signals on anharmonic molecular potential surfaces. We calculate electronic and vibrational dynamics for a number of model systems, showing some results attributed to nonlinearities in spectroscopy experiments (such as breaking of mirror symmetry between absorption and fluorescence signals) and analyzing the influence of nonlinear effects on electronic energy transfer in multi-site aggregates.
一种直接扩展的随机时变变分方法可以将高阶相互作用效应引入电子振动系统的哈密顿量中。这是通过对全局波函数的一个假设来实现的，该假设将振动波包描述为压缩相干态（Davydov 假设的广义版本）。该方法允许对非谐分子势能表面上的量子动力学和光谱信号进行模拟。我们对一些模型系统进行了电子和振动动力学的计算，展示了一些归因于光谱实验中非线性的结果（例如吸收和荧光信号之间的镜像对称性的破坏），并分析了非线性效应对多位置聚集体中电子能量转移的影响。
