Vibrational Spectra of Materials and Molecules from Partially-Adiabatic Elevated-Temperature Centroid Molecular Dynamics

TL;DR

This paper introduces PA-$T_e$-CMD, a new method that improves vibrational spectra calculations by eliminating artifacts and reducing computational costs, applicable to complex molecular systems.

Contribution

It presents a partially-adiabatic implementation of elevated-temperature centroid molecular dynamics that avoids precomputed potentials and enhances spectral accuracy.

Findings

Mitigates the curvature problem in vibrational spectra calculations.

Reduces computational cost compared to traditional path-integral methods.

Performs well on challenging anharmonic systems like CAF and MAPI.

Abstract

Centroid molecular dynamics (CMD) incorporates nuclear quantum statistics into the calculation of vibrational spectra. However, when performed in Cartesian coordinates, CMD shows unphysical artifacts in certain vibrational bands, known as the curvature problem. Recent work showed that CMD spectra can be freed from the curvature problem by evolving the ring-polymer centroid on a potential of mean force (PMF) calculated at an elevated temperature ($T_e$-CMD). Here we present a partially-adiabatic implementation of $T_e$-CMD (PA-$T_e$-CMD), which eliminates the need for precomputed PMFs and instead yields the centroid force 'on the fly'. We introduce a two-temperature path-integral Langevin thermostat to achieve a temperature separation between centroid and internal modes of the ring polymer. Because it is paramount that the elevated temperature be chosen as low as possible for a given physical temperature in this formulation, we present a general scheme for its determination. We benchmark PA-$T_e$-CMD against exact vibrational spectra for the isolated water monomer and discuss its performance for challenging anharmonic systems: the carbonic acid fluoride molecule (CAF) and the methylammonium lead iodide perovskite (MAPI). We conclude that PA-$T_e$-CMD mitigates the curvature problem and the steep increase in computational cost with decreasing temperature of conventional path-integral methods. We observe energy leakage from the hot internal modes to high-frequency centroid modes in some cases, which, nevertheless, only compromises the spectral lineshapes at lower temperatures. While an adiabatic setup based on a coarse-grained centroid PMF is still preferable when a good pre-trained PMF can be easily obtained, PA-$T_e$-CMD presents a low-barrier single-shot setup for any system.