Path-integral calculation of the fourth virial coefficient of helium isotopes

• Published in: The Journal of chemical physics 2021-03, Vol.154 (10), p.104107-104107
• Main Authors: Garberoglio, Giovanni, Harvey, Allan H.
• Format: Article
• Language: English
• Subjects: Exchanging; Helium isotopes; Integrals; Low temperature; Mathematical analysis; Potential energy; Uncertainty; Virial coefficients
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0043446

We use the path-integral Monte Carlo (PIMC) method and state-of-the-art two-body and three-body potentials to calculate the fourth virial coefficients D(T) of 4He and 3He as functions of temperature from 2.6 K to 2000 K. We derive expressions for the contributions of exchange effects due to the bosonic or fermionic nature of the helium isotope; these effects have been omitted from previous calculations. The exchange effects are relatively insignificant for 4He at the temperatures considered, but for 3He, they are necessary for quantitative accuracy below about 4 K. Our results are consistent with previous theoretical work (also with some of the limited and scattered experimental data) for 4He; for 3He, there are no experimental values, and this work provides the first values of D(T) calculated at this level. The uncertainty of the results depends on the statistical uncertainty of the PIMC calculation, the estimated effect of omitting four-body terms in the potential energy, and the uncertainty contribution propagated from the uncertainty of the potentials. At low temperatures, the uncertainty is dominated by the statistical uncertainty of the PIMC calculations, while at high temperatures, the uncertainties related to the three-body potential and omitted higher-order contributions become dominant.