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

Abstract: 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 $^4$He and $^3$He as functions of temperature from 2.6K to 2000K. 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 $^4$He at the temperatures considered, but for $^3$He they are necessary for quantitative accuracy below about 4K. Our results are consistent with previous theoretical work (and with some of the limited and scattered experimental data) for $^4$He; for $^3$He 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 and higher 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 to omitted higher-order contributions become dominant.