On Computing Spectral Densities from Classical, Semiclassical and Quantum Simulations

TL;DR

This paper develops a Fourier-based method to compute spectral densities from semiclassical simulations, enabling quantum effect considerations beyond classical molecular dynamics, with tested protocols showing varying accuracy depending on quantum effects.

Contribution

It introduces two protocols for spectral density calculation from semiclassical simulations, expanding beyond classical methods to include quantum effects.

Findings

Classical LSC-IVR yields highly accurate spectral densities.

Single-trajectory TGWD performs poorly in anharmonic regimes.

Hybrid methods are effective near classical regimes but less so with strong quantum effects.

Abstract

The Caldeira-Leggett model provides a compact characterization of a thermal environment in terms of a spectral density function. This simplicity has led to a variety of numerically exact quantum methods for reduced density matrix propagation. When using these methods, a spectral density has to be computed from dynamical properties of system and environment, which is commonly done using classical molecular dynamics simulations. However, there are situations, where quantum effects could play a role. Therefore, we reformulate our recently developed Fourier method in order to enable spectral density calculations from semiclassical simulations which approximately consider quantum effects. We propose two possible protocols based on either correlation functions or expectation values. These protocols are tested for the linearized semiclassical initial-value representation (LSC-IVR), the thawed Gaussian wave packet dynamics (TGWD) and hybrid schemes combining the two with the more accurate Herman-Kluk (HK) formula. Surprisingly, spectral densities from the LSC-IVR method, based on a completely classical propagation, are extremely accurate whereas those from the single-trajectory TGWD are of poor quality in the anharmonic regime. The hybrid methods provide reasonable quality when the system is close to the classical regime, although, at finite temperature, the computation protocol from expectation values turns out to be more robust. If stronger quantum effects are observed, both hybrid methods turn out as too inaccurate.