Optical line shapes of molecular aggregates: Hierarchical equations of motion method
Optical line shapes of molecular aggregates: Hierarchical equations of motion method
复制标题
分子聚集体的光线形状：层次运动方程法
DOI：
10.1063/1.3213013
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发表时间：
2009-09-07
影响因子：
4.4
通讯作者：
Yan, YiJing
中科院分区：
文献类型：
--
作者：
Chen, Liping;Zheng, Renhui;Yan, YiJing
利用新近发展起来的Liouville空间层次运动方程（HEOM）方法研究了模型分子聚集体的吸收线形状。精确的结果进一步利用几个近似方案，包括高温近似HEOM，随机刘维尔方程的方法，和微扰的时间本地和时间非本地量子主方程（QME）的评估。二聚体，较大的环形聚集体，和模型的B850环在LH2的紫色细菌的计算表明，虽然其他近似的方法可以在很宽的范围内的参数制度，合理的吸收线的形状，二阶时间非局部QME一般是不准确的，可能会给假峰的吸收光谱。
The absorption line shapes of model molecular aggregates are investigated using the recently developed Liouville space hierarchical equations of motion (HEOM) method. The exact results are further exploited for the assessment of several approximation schemes, including the high temperature approximation of HEOM, the stochastic Liouville equation approach, and the perturbative time-local and time-nonlocal quantum master equations (QMEs). The calculations on dimers, larger ring-shaped aggregates, and a model of the B850 ring in the LH2 of purple bacteria show that while the other approximate methods can give reasonable absorption line shapes over a wide range of parameter regimes, the second-order time-nonlocal QME is generally inaccurate and may give spurious peaks in the absorption spectra.