Cook, Lauren E; Runeson, Johan E; Richardson, Jeremy O; Hele, Timothy JH; (2023) Which Algorithm Best Propagates the Meyer-Miller-Stock-Thoss Mapping Hamiltonian for Non-Adiabatic Dynamics? Journal of Chemical Theory and Computation 10.1021/acs.jctc.3c00709. (In press).

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Abstract

A common strategy to simulate mixed quantum-classical dynamics is by propagating classical trajectories with mapping variables, often using the Meyer-Miller-Stock-Thoss (MMST) Hamiltonian or the related spin-mapping approach. When mapping the quantum subsystem, the coupled dynamics reduce to a set of equations of motion to integrate. Several numerical algorithms have been proposed, but a thorough performance comparison appears to be lacking. Here, we compare three time-propagation algorithms for the MMST Hamiltonian: the Momentum Integral (MInt) (J. Chem. Phys., 2018, 148, 102326), the Split-Liouvillian (SL) (Chem. Phys., 2017, 482, 124-134), and the algorithm in J. Chem. Phys., 2012, 136, 084101 that we refer to as the Degenerate Eigenvalue (DE) algorithm due to the approximation required during derivation. We analyze the accuracy of individual trajectories, correlation functions, energy conservation, symplecticity, Liouville's theorem, and the computational cost. We find that the MInt algorithm is the only rigorously symplectic algorithm. However, comparable accuracy at a lower computational cost can be obtained with the SL algorithm. The approximation implicitly made within the DE algorithm conserves energy poorly, even for small timesteps, and thus leads to slightly different results. These results should guide future mapping-variable simulations.

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