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Deriving the exact nonadiabatic quantum propagator in the mapping variable representation

Accepted version
Peer-reviewed

Type

Article

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Authors

Hele, TJH 
Ananth, N 

Abstract

We derive an exact quantum propagator for nonadiabatic dynamics in multi-state systems using the mapping variable representation, where classical-like Cartesian variables are used to represent both continuous nuclear degrees of freedom and discrete electronic states. The resulting Liouvillian is a Moyal series that, when suitably approximated, can allow for the use of classical dynamics to efficiently model large systems. We demonstrate that different truncations of the exact Liouvillian lead to existing approximate semiclassical and mixed quantum-classical methods and we derive an associated error term for each method. Furthermore, by combining the imaginary-time path-integral representation of the Boltzmann operator with the exact Liouvillian, we obtain an analytic expression for thermal quantum real-time correlation functions. These results provide a rigorous theoretical foundation for the development of accurate and efficient classical-like dynamics to compute observables such as electron transfer reaction rates in complex quantized systems.

Description

Keywords

physics.chem-ph, physics.chem-ph, quant-ph

Journal Title

Faraday Discussions

Conference Name

Journal ISSN

1359-6640
1364-5498

Volume Title

195

Publisher

Royal Society of Chemistry