Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
J Chem Phys. 2011 Nov 28;135(20):201101. doi: 10.1063/1.3664763.
An approach for treating dissipative, non-adiabatic quantum dynamics in general model systems at finite temperature based on linearizing the density matrix evolution in the forward-backward path difference for the environment degrees of freedom is presented. We demonstrate that the approach can capture both short time coherent quantum dynamics and long time thermal equilibration in an application to excitation energy transfer in a model photosynthetic light harvesting complex. Results are also presented for some nonadiabatic scattering models which indicate that, even though the method is based on a "mean trajectory" like scheme, it can accurately capture electronic population branching through multiple avoided crossing regions and that the approach offers a robust and reliable way to treat quantum dynamical phenomena in a wide range of condensed phase applications.
本文提出了一种基于线性化环境自由度前向-后向路径差密度矩阵演化的方法,用于处理有限温度下一般模型系统中耗散、非绝热量子动力学。我们证明了该方法可以捕捉短时间相干量子动力学和长时间热平衡,应用于模型光合作用光捕获复合物中的激发能量转移。还给出了一些非绝热散射模型的结果,表明即使该方法基于类似于“平均轨迹”的方案,它也可以准确地捕捉通过多个避免交叉区域的电子布居分支,并且该方法为处理广泛的凝聚相应用中的量子动力学现象提供了一种稳健可靠的方法。