Harmonic Oscillator Staging Coordinates for Efficient Path Integral Simulations of Quantum Oscillators and Crystals.

Abstract

Imaginary-time path integral (PI) is a rigorous quantum mechanical tool to compute static properties at finite temperatures. However, the stiff nature of the internal PI modes poses a sampling challenge. This is commonly tackled using staging coordinates, in which the free particle (FP) contribution of the PI action is diagonalized. We introduce novel and simple staging coordinates that diagonalize the entire action of the harmonic oscillator (HO) model, rendering it efficiently applicable to (exclusively) systems with harmonic character, such as quantum oscillators and crystals. The method is not applicable to fluids or systems with imaginary modes. Unlike FP staging, the HO staging provides a unique treatment of the centroid mode. We provide implementation schemes for PIMC and PIMD simulations in NVT ensemble. Sampling efficiency is assessed in terms of the precision and accuracy of estimating the energy and heat capacity of a one-dimensional HO and an asymmetric anharmonic oscillator (AO). In PIMC, the HO coordinates propose collective moves that perfectly sample the HO contribution, then (for AO) the residual anharmonic term is sampled using standard Metropolis method. This results in a high acceptance rate and, hence, high precision, in comparison to the FP staging. In PIMD, the HO coordinates naturally prescribe definitions for the fictitious masses, yielding equal frequencies of all modes when applied to the HO model. This allows for a substantially larger time step sizes relative to standard staging, without affecting accuracy or integrator stability. For completeness, we also present results using normal mode (NM) coordinates, based on both HO and FP models. While staging and NM coordinates show similar performance (for FP or HO), staging is computationally preferable due to its cheaper scaling with the number of beads. The simplicity and the enhanced sampling gained by the HO coordinates open avenues for efficient estimation of nuclear quantum effects in more complex systems with harmonic character, such as real molecular bonds and quantum crystals.