We propose a trajectory-based quasi-classical method for approximating dynamics in condensed phase systems. Building upon the previously developed optimized mean trajectory approximation that has been used to compute linear and nonlinear spectra, we borrow some ideas from filtering trajectory methods to obtain a novel semiclassical method for the dynamical propagation of density matrices. This new approximation is tested rigorously against standard multistate electronic models, spin-boson models, and models of the Fenna–Matthews–Olson complex. For dissipative systems, the current method is significantly better or as good as many other semiclassical methods available, especially at low temperatures and for off-diagonal density matrix elements, whereas for scattering models, the current method bears similar limitations as mean-field propagation schemes. All results are tested against the numerically exact hierarchical equations of motion method. The new method shows excellent agreement across various parameter regimes with numerically exact results, highlighting the robustness and accuracy of our approach.
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7 December 2024
Research Article|
December 04 2024
A windowed mean trajectory approximation for condensed phase dynamics
Special Collection:
2024 JCP Emerging Investigators Special Collection
Kritanjan Polley
Kritanjan Polley
a)
(Conceptualization, Formal analysis, Investigation, Methodology, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
Chemical Sciences Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
and Department of Chemistry, University of California
, Berkeley, California 94720, USA
a)Author to whom correspondence should be addressed: [email protected]
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Kritanjan Polley
a)
Chemical Sciences Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
and Department of Chemistry, University of California
, Berkeley, California 94720, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 214110 (2024)
Article history
Received:
August 22 2024
Accepted:
November 06 2024
Citation
Kritanjan Polley; A windowed mean trajectory approximation for condensed phase dynamics. J. Chem. Phys. 7 December 2024; 161 (21): 214110. https://doi.org/10.1063/5.0234653
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