Nonadiabatic semiclassical dynamics in the mixed quantum-classical initial value representation.
The Journal of chemical physics
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Church, M. S., Hele, T., Ezra, G. S., & Ananth, N. (2018). Nonadiabatic semiclassical dynamics in the mixed quantum-classical initial value representation.. The Journal of chemical physics, 148 (10), 102326. https://doi.org/10.1063/1.5005557
We extend the Mixed Quantum-Classical Initial Value Representation (MQC-IVR), a semiclassical method for computing real-time correlation functions, to electronically nonadiabatic systems using the Meyer-Miller-Stock-Thoss (MMST) Hamiltonian to treat electronic and nuclear degrees of freedom (dofs) within a consistent dynamic framework. We introduce an efficient symplectic integration scheme, the MInt algorithm, for numerical time-evolution of the nuclear and electronic phase space variables as well as the Monodromy matrix, under the non-separable MMST Hamiltonian. We then calculate the probability of transmission through a curve-crossing in model two-level systems and show that in the quantum limit MQC-IVR is in good agreement with the exact quantum results, whereas in the classical limit the method yields results in keeping with mean-field approaches like the Linearized Semiclassical IVR. Finally, exploiting the ability of MQC-IVR to quantize different dofs to different extents, we present a detailed study of the extents to which quantizing the nuclear and electronic dofs improves numerical convergence properties without significant loss of accuracy.
External DOI: https://doi.org/10.1063/1.5005557
This record's URL: https://www.repository.cam.ac.uk/handle/1810/270834