SELF-CONSISTENT THEORY OF INDUCTION AND DISPERSION FORCES IN THE HARTREE-FOCK APPROXIMATION

A variational derivation is given of non-expanded induction and dispersion energies between many-electron atoms or molecules whose unperturbed ground states are described by Hartree-Fock wavefunctions. Second-order expansion of the perturbed energy gives induction and dispersion as separate Hylleraas functionals which can be minimized with respect to the form of the perturbed spin-orbitals appearing in the first-order trial function. The resulting set of coupled integro-differential equations which determine the best excited spin-orbitals occurring under the interaction can be solved by iteration until self-consistency after expansion of the perturbed orbitals in an appropriate basis. © Taylor & Francis Group, LLC.