R. Moszynski et al., MANY-BODY THEORY OF EXCHANGE EFFECTS IN INTERMOLECULAR INTERACTIONS -DENSITY-MATRIX APPROACH AND APPLICATIONS TO HE-F-, HE-HF, H2-HF, AND AR-H2 DIMERS, The Journal of chemical physics, 100(7), 1994, pp. 5080-5092
The first-order exchange energy for the interactions of closed-shell m
any-electron systems is expanded as a perturbation series with respect
to the Muller-Plesset correlation potentials of the monomers. Explici
t orbital formulas for the leading perturbation corrections are derive
d applying a suitable density matrix formalism. The numerical results
obtained using the Moller-Plesset perturbation expansion, as well as n
onperturbative, coupled-cluster type procedure, are presented for the
interactions of He-F-, He-HF, H-2-HF, and Ar-H-2. It is shown that the
correlation part of the first-order exchange energy increases the unc
orrelated results by 10% to 30% for the investigated range of configur
ations. The analysis of the total interaction energies for selected ge
ometries of these systems shows that at the present level of theory th
e symmetry-adapted perturbation approach correctly accounts for major
intramonomer correlation effects and is capable to accurately reproduc
e the empirical potential energy surfaces.