Physics Department, Zhejiang University, 38 ZheDa Road, Hangzhou, Zhejiang 310027, China.
J Chem Phys. 2013 Jul 28;139(4):044102. doi: 10.1063/1.4812781.
We apply a new formalism to derive the higher-order quantum kinetic expansion (QKE) for studying dissipative dynamics in a general quantum network coupled with an arbitrary thermal bath. The dynamics of system population is described by a time-convoluted kinetic equation, where the time-nonlocal rate kernel is systematically expanded of the order of off-diagonal elements of the system Hamiltonian. In the second order, the rate kernel recovers the expression of the noninteracting-blip approximation method. The higher-order corrections in the rate kernel account for the effects of the multi-site quantum coherence and the bath relaxation. In a quantum harmonic bath, the rate kernels of different orders are analytically derived. As demonstrated by four examples, the higher-order QKE can reliably predict quantum dissipative dynamics, comparing well with the hierarchic equation approach. More importantly, the higher-order rate kernels can distinguish and quantify distinct nontrivial quantum coherent effects, such as long-range energy transfer from quantum tunneling and quantum interference arising from the phase accumulation of interactions.
我们应用一种新的形式主义方法来推导出用于研究与任意热浴耦合的一般量子网络中耗散动力学的高阶量子动力学展开（QKE）。系统种群的动力学由时间卷积的动力学方程描述，其中时间非局部速率核是系统哈密顿量的非对角元素阶数的系统展开。在二阶中，速率核恢复了无相互作用斑点近似方法的表达式。速率核中的高阶修正项考虑了多站点量子相干性和浴弛豫的影响。在量子谐波浴中，解析地推导出了不同阶的速率核。通过四个示例证明，高阶 QKE 可以可靠地预测量子耗散动力学，与层次方程方法相比吻合良好。更重要的是，高阶速率核可以区分和量化不同的非平凡量子相干效应，例如量子隧道中的远程能量转移和相互作用相位积累引起的量子干涉。
