Perturbation theory for the square-well dimer fluid

An analytical equation of state is presented for the square-well dimer fluid of variable well width (1 ≤ λ ≤ 2) based on Barker-Henderson perturbation theory using the recently developed analytical expression for radial distribution function of hard dimers. The integral in the first- and the second-order perturbation terms utilizes the Tang, Y. and Lu, B. C.-Y., 1994, J. chem. Phys., 100, 6665 formula for the Hilbert transform. To test the equation of state, NVT and Gibbs ensemble Monte Carlo simulations for square-well dimer fluids are performed for three different well widths (λ = 1.3, 1.5 and 1.8). The prediction of the perturbation theory is also compared with that of thermodynamic perturbation theory in which the equation of state for the square-well dimer is written in terms of that of square-well monomers and the contact value of the radial distribution function.