Exact quantum statistics for electronically nonadiabatic systems using continuous path variables

Abstract

We derive an exact, continuous-variable path integral (PI) representation of the canonical partition function for electronically nonadiabatic systems. Utilizing the Stock–Thoss (ST) mapping for an N-level system, matrix elements of the Boltzmann operator are expressed in Cartesian coordinates for both the nuclear and electronic degrees of freedom. The PI discretization presented here properly constrains the electronic Cartesian coordinates to the physical subspace of the mapping. We numerically demonstrate that the resulting PI–ST representation is exact for the calculation of equilibrium properties of systems with coupled electronic and nuclear degrees of freedom. We further show that the PI–ST formulation provides a natural means to initialize semiclassical trajectories for the calculation of real-time thermal correlation functions, which is numerically demonstrated in applications to a series of nonadiabatic model systems.

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