A partially linearized spin-mapping approach for simulating nonlinear optical spectra

TL;DR

This paper introduces a partially linearized spin-mapping method for simulating both linear and nonlinear optical spectra in large condensed-phase systems, capturing quantum coherence effects with high accuracy.

Contribution

The paper develops a novel spin-PLDM approach that improves accuracy in optical spectra simulations and enables pathway decomposition for detailed spectral analysis.

Findings

Accurately computes pump--probe and 2D spectra for complex systems.

Demonstrates superior performance over existing classical-trajectory methods.

Provides detailed insights into Liouville-space pathways.

Abstract

We present a partially linearized method based on spin mapping for computing both linear and nonlinear optical spectra. As observables are obtained from ensembles of classical trajectories, the approach can be applied to the large condensed-phase systems that undergo photosynthetic light-harvesting processes. In particular, the recently derived spin-PLDM method has been shown to exhibit superior accuracy in computing population dynamics compared to other related classical-trajectory methods. Such a method should also be ideally suited to describing the quantum coherences generated by interaction with light. We demonstrate that this is indeed the case by calculating the nonlinear optical response functions relevant for the pump--probe and 2D photon-echo spectra for a Frenkel biexciton model and the Fenna--Matthews--Olsen light-harvesting complex. One especially desirable feature of our approach is that the full spectrum can be decomposed into its constituent components associated with the various Liouville-space pathways, offering a greater insight beyond what can be directly obtained from experiment.