Liquid-vapor isotopic fractionation factors of diatomic fluids: a direct comparison between molecular simulation and experiment.

Liquid-vapor fractionation factors of molecular fluids are studied by molecular-based simulation, Gibbs ensemble Monte Carlo, and isothermal-isochoric molecular dynamics of realistic models for N(2), O(2), and CO. The temperature dependence of the fractionation factors for (15)N(14)N(14)N(2), (15)N(2)(14)N(2), (18)O(16)O(16)O(2), (18)O(2)(16)O(2), (13)C(16)O(12)C(16)O, and (12)C(18)O(12)C(16)O along the vapor-liquid coexistence curves as predicted by simulation is compared with the existing experimental data to assess the accuracy of Planck's(2)-order Kirkwood-Wigner free energy expansion for specific model parametrizations. Predictions of the fractionation factors for other isotopologue pairs, including (18)O(17)O(16)O(2), (16)O(17)O(16)O(2), and (17)O(2)(16)O(2), as well as tests of some approximations behind the microscopic interpretation of the fractionation factors are also given.