Sensitivity of the thermal and acoustic virial coefficients of argon to the argon interaction potential.
Second, third, and fourth thermal and acoustic virial coefficients between 100 and 1000 K are computed for different argon interaction models derived from combinations of accurate two- and three-body potentials. Differences between the various interaction models tested mirror the presumed order in the accuracy of these models, but are not well captured at the level of the lowest-order contributions in the virial expansion: While the second- and third-order virial coefficients are found to be rather insensitive to small variations in the two- and three-body potentials, more pronounced differences in higher-order coefficients are currently of limited use in assessing the accuracy of the interaction potential due to difficulties in the unambiguous experimental determination of these higher-order coefficients. In contrast, pressure-volume and speed-of-sound data--both of which are experimentally known to highest accuracies--are found to be insensitive to small variations in the interaction model. All but the least accurate models reproduce experimental pressure-volume and speed-of-sound data near-quantitatively in regions where the (fourth-order) virial expansions apply. All quantities considered are found to be completely unaffected by a non-vanishing quadruple-dipole four-body potential.
Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University Albany, Private Bag 102904, Auckland 0745, New Zealand. j.wiebke@massey.ac.nz
Jonas
J
Wiebke
Elke
E
Pahl
Peter
P
Schwerdtfeger