Perturbation theory of the electron correlation effects for atomic and molecular properties. Second- and third-order correlation corrections to molecular dipole moments and polarizabilities

Abstract

The many-body perturbation theory is applied for the calculation of the second- and third-order correlation corrections to the SCF HF dipole moments and polarizabilities of FH, H2O, NH3, and CH4. All calculations are performed by using the finite-field perturbation approach. The pertinent correlation corrections follow from the numerical differentiation of the second- and third-order field-dependent correlation energies. This computational scheme corresponds to a completely self-consistent treatment of the perturbation effects. The third-order corrected dipole moments are in excellent agreement with the experimental data and the best results of other authors. A comparison of the present perturbation corrections for polarizabilities with the PNO–CI and CEPA results of Werner and Meyer reveals that some cancellation of the third- and fourth-order correlation contributions can be expected. The second-order corrected polarizabilities are as a rule better than the results of the third-order perturbation approach. It is concluded that also for polarizabilities the low-order many-body perturbation scheme is able to account for the major portion of the relevant correlation effects.