We have obtained by Monte Carlo NVT simulations the constant-volume excess
heat capacity of square-well fluids for several temperatures, densities and
potential widths. Heat capacity is a thermodynamic property much more sensitive
to the accuracy of a theory than other thermodynamic quantities, such as the
compressibility factor. This is illustrated by comparing the reported
simulation data for the heat capacity with the theoretical predictions given by
the Barker-Henderson perturbation theory as well as with those given by a
non-perturbative theoretical model based on Baxter's solution of the
Percus-Yevick integral equation for sticky hard spheres. Both theories give
accurate predictions for the equation of state. By contrast, it is found that
the Barker-Henderson theory strongly underestimates the excess heat capacity
for low to moderate temperatures, whereas a much better agreement between
theory and simulation is achieved with the non-perturbative theoretical model,
particularly for small well widths, although the accuracy of the latter worsens
for high densities and low temperatures, as the well width increases.Comment: 11 pages, 4 figures; figures now include additional perturbation
data; to be published in Mol. Phy