Polarization effects on intermolecular vibrational energy transfer analyzed by 2DIR spectroscopy

TL;DR

This paper investigates how polarization effects influence 2DIR spectroscopy measurements of intermolecular vibrational energy transfer, emphasizing the role of rotational diffusion in spectral distortions and their implications for interpreting third-order optical processes.

Contribution

It provides a detailed analysis of polarization effects and spectral distortions caused by rotational diffusion in 2DIR experiments on vibrational energy transfer systems.

Findings

Spectral distortions depend on rotational diffusion constants.

Polarization effects significantly influence 2DIR spectral interpretation.

Conclusions are applicable to other third-order optical processes.

Abstract

In the present work, we analyze the influence of the polarization effects taking place during the course of a 2DIR spectroscopy experiment performed on a molecular system undergoing an intermolecular vibrational energy transfer process. When both donor and acceptor molecules participating in the vibrational energy transfer are embedded in a host solvent, they face rotational diffusion that strongly distorts the resulting 2DIR spectra. It could be expected that the difference between rotational diffusion constants will be of particular interest. For this purpose, the polarization effects are discussed according to the different orderings of the laser-molecule interactions. Next, we study the distortions of the spectra as a function of the rotational diffusion constants of the individual molecules. The knowledge of these polarization effects are relevant to the interpretation of the spectra. Finally, the conclusions reached in this work for a vibrational energy transfer are valid for any other type of third-order optical process performed on the same molecular system.