Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
J Chem Phys. 2012 Jun 14;136(22):224103. doi: 10.1063/1.4724193.
We present an optimized hierarchical equations of motion theory for quantum dissipation in multiple Brownian oscillators bath environment, followed by a mechanistic study on a model donor-bridge-acceptor system. We show that the optimal hierarchy construction, via the memory-frequency decomposition for any specified Brownian oscillators bath, is generally achievable through a universal pre-screening search. The algorithm goes by identifying the candidates for the best be just some selected Padé spectrum decomposition based schemes, together with a priori accuracy control criterions on the sole approximation, the white-noise residue ansatz, involved in the hierarchical construction. Beside the universal screening search, we also analytically identify the best for the case of Drude dissipation and that for the Brownian oscillators environment without strongly underdamped bath vibrations. For the mechanistic study, we quantify the quantum nature of bath influence and further address the issue of localization versus delocalization. Proposed are a reduced system entropy measure and a state-resolved constructive versus destructive interference measure. Their performances on quantifying the correlated system-environment coherence are exemplified in conjunction with the optimized hierarchical equations of motion evaluation of the model system dynamics, at some representing bath parameters and temperatures. Analysis also reveals the localization to delocalization transition as temperature decreases.
我们提出了一种优化的多布朗运动振子浴环境下量子耗散的层次运动方程理论，并对模型供体-桥-受体体系进行了机理研究。我们表明，通过对任意指定的布朗运动振子浴进行记忆-频率分解，可以通过通用的预筛选搜索来实现最优的层次结构构建。该算法通过识别最佳的候选者来实现，这些候选者基于一些选定的 Padé 谱分解方案，并结合层次结构构建中唯一的近似值——白噪声残差假设的先验精度控制标准。除了通用的筛选搜索之外，我们还针对德劳德耗散和没有强过阻尼浴振动的布朗运动振子环境的情况，分析确定了最佳的情况。对于机理研究，我们量化了浴影响的量子性质，并进一步解决了局域化与非局域化的问题。提出了一种简化的系统熵测度和一种状态分辨的建设性与破坏性干涉测度。它们在结合模型系统动力学的优化层次运动方程评估来量化相关系统-环境相干性方面的性能，在一些代表性的浴参数和温度下进行了示例。分析还揭示了随着温度的降低从局域化到非局域化的转变。
