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

J Chem Phys

Applied Chemicals and Materials Division, National Institute of Standards and Technology, Boulder, Colorado 80305, USA.

Published: March 2021

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 He and He 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 He at the temperatures considered, but for He, 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 He; for 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 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.

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8358982PMC
http://dx.doi.org/10.1063/5.0043446DOI Listing

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