Efficient "on-the-fly" calculation of Raman spectra from \textit{ab-initio} molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

TL;DR

This paper introduces a highly efficient computational method for calculating Raman spectra directly from ab-initio molecular dynamics, enabling routine finite-temperature spectral predictions for solutes in water.

Contribution

The authors develop a novel on-the-fly calculation scheme that significantly improves efficiency of Raman spectra computation from first principles.

Findings

Successfully applied to hydrophobic and hydrophilic solutes in water

Achieves at least tenfold increase in computational efficiency

Accurately predicts infrared and Raman spectral changes due to solutes

Abstract

We present a computational method to accurately calculate Raman spectra from first principles with an at least one order of magnitude higher efficiency. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of \textit{ab-initio} molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra.