Generalized quantum kinetic expansion: Time scale separation between intra-cluster and inter-cluster kinetics
- Physics Department, Zhejiang University, 38 ZheDa Road, Hangzhou, Zhejiang 310027 (China)
For a general two-cluster network, a new methodology of the cluster-based generalized quantum kinetic expansion (GQKE) is developed in the matrix formalism under two initial conditions: the local cluster equilibrium and system-bath factorized states. For each initial condition, the site population evolution follows exactly a distinct closed equation, where all the four terms involved are systematically expanded over inter-cluster couplings. For the system-bath factorized initial state, the numerical investigation of the two models, a biased (2, 1)-site system and an unbiased (2, 2)-site system, verifies the reliability of the GQKE and the relevance of higher-order corrections. The time-integrated site-to-site rates and the time evolution of site population reveal the time scale separation between intra-cluster and inter-cluster kinetics. The population evolution of aggregated clusters can be quantitatively described by the approximate cluster Markovian kinetics.
- OSTI ID:
- 22489559
- Journal Information:
- Journal of Chemical Physics, Vol. 143, Issue 10; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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