Simulating vibronic spectra via Matsubara-like dynamics: Coping with the sign problem.

Abstract

Measuring vibronic spectra probes dynamical processes in molecular systems. When interpreted via suitable theoretical tools, the experimental data provides comprehensive information about the system in question. For complex many-body problems, such an approach usually requires the formulation of proper classical-like approximations, which is particularly challenging if multiple electronic states are involved. In this work, we express the imaginary-time shifted time correlation function and, thus, the vibronic spectrum in terms of the so-called Matsubara dynamics, which combines quantum statistics and classical-like dynamics. By applying the Matsubara approximation in the adiabatic limit, we derive a formal generalization of the existing Matsubara dynamics formalism to multiple potential energy surfaces (PESs), which, however, does not feature all the defining properties of its single-PES counterpart though suffering equally from the sign problem. The mathematical analysis for two shifted harmonic oscillators suggests a new modified method to practically simulate the standard correlation function via Matsubara-like dynamics. Importantly, this modified method samples the thermal Wigner function without suffering from the sign problem and yields an accurate approximation to the vibronic absorption spectrum, not only for the harmonic system but also for the anharmonic one.