MBPT studies of van der Waals molecules

Abstract

The many-body perturbation theory is employed for the calculation of the interaction potential for the F^- … He system in the framework of the supermolecule method. A particular attention is paid to the choice of the basis set functions for the two subsystems and the related basis set superposition effects. It has been found that the main features of the interaction potential are recovered in the SCF approximation. The SCF potential has its minimum at the distance R = 6·4 a ₀ with the interaction energy of 53 cm^-1. The complete fourth-order MBPT method gives the potential minimum position and depth equal to 6·5 a ₀ and 64 cm^-1, respectively. The basis set superposition effects estimated by using the counterpoise technique are negligibly small for the SCF interaction potential, while at the correlated level their magnitude is comparable to the value of the total correlation contribution to the interaction energy. The basis set superposition effect in calculations of the electron correlation contribution to weak intermolecular interactions is found to be the major factor limiting the reliability of the corresponding theoretical data.