Rigorous Quantum Thermodynamics from Entropic Path Integral Coarse-Graining

TL;DR

EPIGS is a new method that enables accurate quantum thermodynamics simulations using classical computational resources by training effective potentials with an instanton-based free-energy scheme.

Contribution

Introduces entropic path-integral coarse-graining (EPIGS), a scalable method for rigorous quantum thermodynamics using classical simulations with transferable potentials.

Findings

EPIGS reproduces quantum free energies within 0.2 meV/atom.

Benchmarks show EPIGS matches full path-integral results for hydrogen-bonded systems.

EPIGS is computationally efficient and applicable across temperatures.

Abstract

Nuclear quantum effects (NQEs) remain a major challenge for molecular simulations, as rigorous treatment requires imaginary-time path-integral methods with heavy computational overhead. Neglecting NQEs leads to systematic errors in thermodynamic properties and failures in predicting isotope effects, quantum tunnelling, and anharmonic zero-point motion. Here, we introduce entropic path-integral coarse-graining (EPIGS), which enables rigorous quantum thermodynamics at the cost of classical simulations by training size- and temperature-transferable effective potentials utilising absolute centroid free energy and entropy. Central to EPIGS is an instanton-based free-energy perturbation scheme that enables efficient and accurate evaluation of the centroid free energy and entropy for large systems, making construction of the EPIGS training dataset practical. Benchmarks against full path-integral simulations on representative hydrogen-bonded systems, including liquid water, show that EPIGS reproduces quantum free energies and enthalpies within 0.2 meV/atom at near-classical computational cost. EPIGS provides a highly accurate, scalable and low-cost framework for quantum thermodynamic simulations of complex systems across temperatures.