One-Shot Simulation of Static Disorder in Quantum Dynamics with Equilibrium Initial State via Matrix Product State Sampling

Abstract

Static disorder plays a crucial role in the electronic dynamics and spectroscopy of complex molecular systems. Traditionally, obtaining observables averaged over static disorder requires thousands of realizations via direct sampling of the disorder distribution, leading to high computational costs. In this work, we extend the auxiliary degree-of-freedom based matrix product state (MPS) method to handle system-bath correlated thermal equilibrium initial states. We validate the effectiveness of the extended method by computing the dipole-dipole time correlation function of the Holstein model relevant to the emission spectrum of molecular aggregates. Our results show that the method accurately captures static disorder effects using a one-shot quantum dynamical simulation, with only a moderate increase in MPS bond dimension, thereby significantly reducing computational cost. Moreover, it enables the generation of a much larger number of samples than the conventional direct sampling method at negligible additional cost, thus reducing statistical errors. This method provides a broadly useful tool for calculating equilibrium time correlation functions in system-bath coupled models with static disorder.