Spectroscopic response theory with classical mapping Hamiltonians.

Abstract

Exact quantum dynamics with a time-independent Hamiltonian in a discrete state space can be computed using classical mechanics through the classical Meyer-Miller-Stock-Thoss mapping Hamiltonian. In order to compute quantum response functions from classical dynamics, we extend this mapping to a quantum Hamiltonian with time-dependence arising from a classical field. This generalization requires attention to time-ordering in quantum and classical propagators. Quantum response theory with the original quantum Hamiltonian is equivalent to classical response theory with the classical mapping Hamiltonian. We elucidate the structure of classical response theory with the mapping Hamiltonian, thereby generating classical versions of the two-sided quantum density operator diagrams conventionally used to describe spectroscopic processes. This formal development can provide a foundation for new semiclassical approximations to spectroscopic observables for models in which classical nuclear degrees of freedom are introduced into a mapping Hamiltonian describing electronic states. Calculations of the temperature-dependence of two-dimensional electronic spectra for an exciton dimer using two semiclassical approaches are compared with benchmark calculations using the hierarchical equations of motion method.