Path-integral calculation of the third dielectric virial coefficient of noble gases

TL;DR

This paper introduces a quantum path-integral Monte Carlo framework to accurately compute the third dielectric virial coefficient of noble gases, advancing theoretical predictions for gas properties relevant to metrology.

Contribution

First fully quantum computational framework for the third dielectric virial coefficient of noble gases, including exchange effects, using path-integral Monte Carlo methods.

Findings

Results align with existing experimental data for helium, neon, and argon.

Highlights the need for improved three-body potential surfaces for better accuracy.

Establishes a foundation for first-principles gas property calculations in metrology.

Abstract

We present the first framework for fully quantum calculation of the third dielectric virial coefficient $C_\varepsilon(T)$ of noble gases, including exchange effects. The quantum effects are taken into account with the path-integral Monte Carlo method. Calculations employing state-of-the-art pair and three-body potentials and pair polarizabilities yield results generally consistent with the few scattered experimental data available for helium, neon, and argon, but rigorous calculations with well-described uncertainties will require the development of surfaces for the three-body nonadditive polarizability and the three-body dipole moment. The framework developed here will enable new approaches to primary temperature and pressure metrology based on first-principles calculations of gas properties.