The Nakajima-Zwanzig generalized master equation provides a formally exact framework to simulate quantum dynamics in condensed phases. Yet, the exact memory kernel is hard to obtain and calculations based on perturbative expansions are often employed. By using the spin-boson model as an example, we assess the convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation. The exact memory kernels are calculated by combining the hierarchical equation of motion approach and the Dyson expansion of the exact memory kernel. High order expansions of the memory kernels are obtained by extending our previous work to calculate perturbative expansions of open system quantum dynamics [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. It is found that the high order expansions do not necessarily converge in certain parameter regimes where the exact kernel show a long memory time, especially in cases of slow bath, weak system-bath coupling, and low temperature. Effectiveness of the Padé and Landau-Zener resummation approaches is tested, and the convergence of higher order rate constants beyond Fermi’s golden rule is investigated.
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Convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation and rate constants: Case study of the spin-boson model
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28 April 2018
Research Article|
April 24 2018
Convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation and rate constants: Case study of the spin-boson model
Meng Xu
;
Meng Xu
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
and University of Chinese Academy of Sciences
, Beijing 100049, China
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Yaming Yan;
Yaming Yan
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
and University of Chinese Academy of Sciences
, Beijing 100049, China
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Yanying Liu
;
Yanying Liu
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
and University of Chinese Academy of Sciences
, Beijing 100049, China
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Qiang Shi
Qiang Shi
a)
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
and University of Chinese Academy of Sciences
, Beijing 100049, China
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,
,
,
Yaming Yan
Yanying Liu
Qiang Shi
a)
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
and University of Chinese Academy of Sciences
, Beijing 100049, China
J. Chem. Phys. 148, 164101 (2018)
Article history
Received:
January 18 2018
Accepted:
March 23 2018
Citation
Meng Xu, Yaming Yan, Yanying Liu, Qiang Shi; Convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation and rate constants: Case study of the spin-boson model. J. Chem. Phys. 28 April 2018; 148 (16): 164101. https://doi.org/10.1063/1.5022761
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