Relaxation and fluctuation dynamics in coherent two-dimensional electronic spectra

TL;DR

This paper develops a comprehensive theoretical framework using cumulant expansion to describe the interplay of relaxation and fluctuation dynamics in 2D electronic spectra, highlighting their interdependence and conditions for simplified models.

Contribution

It introduces a response function approach that simultaneously accounts for population transfer and fluctuation dynamics in 2D spectroscopy, bridging a gap in existing theoretical models.

Findings

Population transfer and fluctuation dynamics are generally interdependent.

The proposed method aligns with the modified Redfield theory.

Conditions for when simplified models are valid are identified.

Abstract

Two-dimensional (2D) spectroscopy provides information about dissipative processes subsequent to electronic excitation, which play a functional role in energy harvesting materials and devices. This technique is particularly sensitive to electronic and vibronic coherence dynamics. While the theoretical treatment of relaxation in the context of 2D-spectroscopy is well-developed under the assumption of different timescales of population transfer and fluctuation dynamics, the interplay between both kinds of processes lacks a comprehensive description in terms of line shape functions. To bridge this gap, we use the cumulant expansion approach to derive response functions, which account for fluctuation dynamics and population transfer simultaneously. We compare 2D-spectra from calculations with different model assumptions about correlations between fluctuations and point out under which conditions a simplified treatment is justified. Our study shows that population transfer and dissipative fluctuation dynamics cannot be described independent of each other in general. Advantages and limitations of the proposed calculation method and its compatibility with the modified Redfield description are discussed.