2D spectroscopies from condensed phase dynamics: Accessing third-order response properties from equilibrium multi-time correlation functions

TL;DR

This paper presents a new method to compute third-order spectroscopic responses from equilibrium multi-time correlation functions, enabling better interpretation of nonlinear condensed phase spectroscopies.

Contribution

It formulates third-order response functions in terms of equilibrium symmetrized Kubo transformed correlation functions, compatible with classical and quantum dynamics methods.

Findings

Accurately captures anharmonic spectral features

Demonstrates effectiveness with classical and RPMD simulations

Provides a transparent framework for multidimensional spectroscopy analysis

Abstract

The third-order response lies at the heart of simulating and interpreting nonlinear spectroscopies ranging from two dimensional infrared (2D-IR) to 2D electronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra time and frequency dimensions in these spectroscopies provides access to rich information on the electronic and vibrational states present, the coupling between them, and the resulting rates at which they exchange energy that are obscured in linear spectroscopy, particularly for condensed phase systems that usually contain many overlapping features. While the exact quantum expression for the third-order response is well established it is incompatible with the methods that are practical for calculating the atomistic dynamics of large condensed phase systems. These methods, which include both classical mechanics and quantum dynamics methods that retain quantum statistical properties while obeying the symmetries of classical dynamics, such as LSC-IVR, Centroid Molecular Dynamics (CMD) and Ring Polymer Molecular Dynamics (RPMD) naturally provide short-time approximations to the multi-time symmetrized Kubo transformed correlation function. Here, we show how the third-order response can be formulated in terms of equilibrium symmetrized Kubo transformed correlation functions. We demonstrate the utility and accuracy of our approach by showing how it can be used to obtain the third-order response of a series of model systems using both classical dynamics and RPMD. In particular, we show that this approach captures features such as anharmonically induced vertical splittings and peak shifts while providing a physically transparent framework for understanding multidimensional spectroscopies.