Efficient construction of generalized master equation memory kernels for multi-state systems from nonadiabatic quantum-classical dynamics

Pfalzgraff, William C.; Montoya-Castillo, Andrés; Kelly, Aaron; Markland, Thomas E.

doi:10.1063/1.5095715

Title: Efficient construction of generalized master equation memory kernels for multi-state systems from nonadiabatic quantum-classical dynamics

Journal Article · Tue Jun 25 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5095715· OSTI ID:1577593

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Stanford Univ., CA (United States); Chatham University, Pittsburgh, PA (United States)
Stanford Univ., CA (United States)
Dalhousie Univ., Halifax, NS (Canada)

Techniques derived from the generalized quantum master equation (GQME) framework have provided the basis for elucidating energy and charge transfer in systems ranging from molecular solids to photosynthetic complexes. Recently, the nonperturbative combination of the GQME with quantum-classical methods has resulted in approaches whose accuracy and efficiency exceed those of the original quantumclassical schemes while offering significant accuracy improvements over perturbative expansions of the GQME. In this work, we show that, while the non-Markovian memory kernel required to propagate the GQME scales quartically with the number of subsystem states, the number of trajectories required scales at most quadratically when using quantum-classical methods to construct the kernel. We then present an algorithm that allows further acceleration of the quantum-classical GQME by offering a way to selectively sample the kernel matrix elements that are most important to the process of interest. We demonstrate the utility of these advances by applying the combination of Ehrenfest mean field theory with the GQME (MF-GQME) to models of the Fenna-Matthews-Olson (FMO) complex and the light harvesting complex II (LHCII), with 7 and 14 states, respectively. This allows us to show that the MF-GQME is able to accurately capture all the relevant dynamical time scales in LHCII: the initial nonequilibrium population transfer on the femtosecond time scale, the steady state-type trapping on the picosecond time scale, and the long time population relaxation. Remarkably, all of these physical effects spanning tens of picoseconds can be encoded in a memory kernel that decays only after ~65 fs.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Univ. of California, Merced, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0014437

OSTI ID:: 1577593

Alternate ID(s):: OSTI ID: 1529414

Journal Information:: Journal of Chemical Physics, Vol. 150, Issue 24; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Quantum chemical dynamics
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