From Classical to Quantum and Back: Hamiltonian Adaptive Resolution Path Integral, Ring Polymer, and Centroid Molecular Dynamics

TL;DR

This paper introduces a Hamiltonian-based adaptive resolution method that combines classical and quantum path integral techniques, enabling efficient simulations of quantum effects in complex systems with reduced computational cost.

Contribution

It extends previous Hamiltonian adaptive resolution approaches to include ring polymer and centroid molecular dynamics, along with a new integration algorithm utilizing multiple time-stepping.

Findings

Validated via adaptive classical-path-integral simulations of water

Demonstrated potential for efficient quantum simulations of interfaces

Applicable to complex biomolecular systems

Abstract

Path integral-based simulation methodologies play a crucial role for the investigation of nuclear quantum effects by means of computer simulations. However, these techniques are significantly more demanding than corresponding classical simulations. To reduce this numerical effort, we recently proposed a method, based on a rigorous Hamiltonian formulation, which restricts the quantum modeling to a small but relevant spatial region within a larger reservoir where particles are treated classically. In this work, we extend this idea and show how it can be implemented along with state-of-the-art path integral simulation techniques, such as ring polymer and centroid molecular dynamics, which allow the approximate calculation of both quantum statistical and quantum dynamical properties. To this end, we derive a new integration algorithm which also makes use of multiple time-stepping. The scheme is validated via adaptive classical--path-integral simulations of liquid water. Potential applications of the proposed multiresolution method are diverse and include efficient quantum simulations of interfaces as well as complex biomolecular systems such as membranes and proteins.