Two-dimensional electronic spectra from the hierarchical equations of motion method: Application to model dimers.
Two-dimensional electronic spectra from the hierarchical equations of motion method: Application to model dimers.
复制标题
DOI：
10.1063/1.3293039
复制
发表时间：
2010-01
期刊：
影响因子：
--
通讯作者：
Liping Chen;Ren-hui Zheng;Qiang Shi;Yijing Yan
中科院分区：
文献类型：
--
作者：
Liping Chen;Ren-hui Zheng;Qiang Shi;Yijing Yan
我们扩展了我们以前用Liouville空间分级运动方程（HEOM）方法对分子聚集体吸收线形状的研究[L。陈佩，R. H.郑角Shi和Y. J.Yan，J.Chem.Phys.131，094502（2009）]来计算模型二聚体的三阶光学响应函数和二维电子光谱。在我们以前的工作中，我们专注于几个近似方法的适用性相关的HEOM方法。我们发现，虽然二阶微扰量子主方程在描述峰形和溶剂化动力学方面通常是不准确的，但即使在中间耦合区，它们也可以给出合理的峰振幅演化。随机刘维尔方程的结果在良好的峰形，但不正确地描述激发态动力学由于缺乏详细的平衡。一个修改后的版本的高温近似的HEOM给出了最好的协议与确切的结果。
We extend our previous study of absorption line shapes of molecular aggregates using the Liouville space hierarchical equations of motion (HEOM) method [L. P. Chen, R. H. Zheng, Q. Shi, and Y. J. Yan, J. Chem. Phys. 131, 094502 (2009)] to calculate third order optical response functions and two-dimensional electronic spectra of model dimers. As in our previous work, we have focused on the applicability of several approximate methods related to the HEOM method. We show that while the second order perturbative quantum master equations are generally inaccurate in describing the peak shapes and solvation dynamics, they can give reasonable peak amplitude evolution even in the intermediate coupling regime. The stochastic Liouville equation results in good peak shapes, but does not properly describe the excited state dynamics due to the lack of detailed balance. A modified version of the high temperature approximation to the HEOM gives the best agreement with the exact result.