Efficacious calculation of Raman spectra in high pressure hydrogen

TL;DR

This paper introduces a fast, mode-free method for simulating Raman spectra from molecular dynamics, enabling analysis of high-temperature high-pressure hydrogen where traditional normal mode approaches fail.

Contribution

The paper presents a novel, efficient approach for calculating Raman spectra directly from MD trajectories without normal mode analysis, applicable to complex, high-temperature phases.

Findings

Method significantly speeds up Raman spectra calculations

Identifies symmetry-breaking regimes in high-pressure hydrogen

Spectra features align with experimental resolution limits

Abstract

We present and evaluate an efficient method for simulating Raman spectra from molecular dynamics (MD) calculations {\it without} defining normal modes. We apply the method to high pressure hydrogen in the high-temperature "Phase IV": a plastic crystal in which the conventional picture of fixed phonon eigenmodes breaks down. Projecting trajectories onto in-phase molecular stretches is shown to be many orders of magnitude faster than polarisability calculations, allowing statistical averaging at high-temperature. The simulations are extended into metastable regimes and identify several regimes associated with symmetry-breaking on different timescales, which are shown to exhibit features in the Raman spectra at the current experimental limit of resolvability. In this paper we have concentrated on the methodology, a fuller description of the structure of Phase IV hydrogen is given in a previous paper