Spectral line shapes in linear absorption and two-dimensional spectroscopy with skewed frequency distributions.

Abstract

The effect of Gaussian dynamics on the line shapes in linear absorption and two-dimensional correlation spectroscopy is well understood as the second-order cumulant expansion provides exact spectra. Gaussian solvent dynamics can be well analyzed using slope line analysis of two-dimensional correlation spectra as a function of the waiting time between pump and probe fields. Non-Gaussian effects are not as well understood, even though these effects are common in nature. The interpretation of the spectra, thus far, relies on complex case to case analysis. We investigate spectra resulting from two physical mechanisms for non-Gaussian dynamics, one relying on the anharmonicity of the bath and the other on non-linear couplings between bath coordinates. These results are compared with outcomes from a simpler log-normal dynamics model. We find that the skewed spectral line shapes in all cases can be analyzed in terms of the log-normal model, with a minimal number of free parameters. The effect of log-normal dynamics on the spectral line shapes is analyzed in terms of frequency correlation functions, maxline slope analysis, and anti-diagonal linewidths. A triangular line shape is a telltale signature of the skewness induced by log-normal dynamics. We find that maxline slope analysis, as for Gaussian dynamics, is a good measure of the solvent dynamics for log-normal dynamics.