Numerically-Exact Quantum-Simulation Approach for Two-Dimensional Spectroscopy of Open Quantum Systems

TL;DR

This paper introduces a numerically-exact quantum simulation method for two-dimensional spectroscopy of open quantum systems, enabling precise analysis of complex dynamics and system-bath interactions.

Contribution

It develops a bath-engineering technique-based approach for efficient, accurate 2DS simulations, demonstrated on a four-level system and a real molecular system.

Findings

Successfully simulated 2DS of a four-level system in chiral enantiodetection.

Reproduced experimental spectral patterns of RDC in chloroform.

Assessed the center-line slope method for extracting time correlation functions.

Abstract

Two-dimensional spectroscopy (2DS) is a powerful ultrafast technique for probing electronic and vibrational dynamics in complex microscopic systems. Extracting detailed information on system dynamics and system-bath interactions from 2DS experiments requires precise theoretical simulations for comparison, which motivates the development of numerically-exact and computationally-efficient simulation approaches. Here, we propose a quantum-simulation approach for 2DS based on the bath-engineering technique (BET), which has been successfully employed in quantum simulations of open quantum dynamics. To demonstrate our approach, we first simulate the 2DS of a driven four-level system in chiral enantiodetection, where we also assess the applicability of the center-line slope (CLS) method for extracting time correlation functions (TCFs) from the 2DS. We further apply our approach to the 2DS of ${\rm Rh(CO)_2C_5H_7O_2}$ (RDC) dissolved in chloroform, where the results reproduce the main spectral patterns observed in experiments. Our work provides a numerically-exact and efficient framework for simulating 2DS, and can offer additional insight into the dynamics of open quantum systems.