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

Abstract: Centroid molecular dynamics (CMD) incorporates nuclear quantum statistics into the calculation of vibrational spectra. However, when performed in Cartesian coordinates, CMD shows serious 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 \textit{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 eliminates the steep increase in computational cost with decreasing temperature of conventional path-integral methods. We observe some energy leakage from the hot internal modes to high-frequency centroid modes at low physical temperatures. Nevertheless, compared to other imaginary path-integral approximate methods, the PA-$T_e$-CMD spectra show more accurate lineshapes. While a fully 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.