Van der Waals potentials of He2, Ne2, and Ar2 with the exchange energy calculated by the surface integral method

A simple semiempirical potential for two-body multielectron systems is developed. The repulsion is obtained from the exchange energy that is calculated with the surface integral method. The main component of the attraction comes from the second-order polarization energy given by the damped dispersion series. The small contributions of the first-order polarization energy and the overlap integrals to the van der Waals potential are examined. Without any adjustable parameters, this theory is shown to give accurate potential curves for the He2, Ne2, and Ar2 systems. By absorbing the first-order polarization energy into the exchange energy expression and neglecting the small contribution of the overlap integrals, this theory reduces to the successful Tang–Toennies potential model.