A post-Hartree-Fock model of intermolecular interactions:Inclusion of higher-order corrections

摘要

We have previously demonstrated that the dipole moment of the exchange hole can be used to derive intermolecular C_6 dispersion coefficients[J.Chem.Phys.122,154104(2005)].This was subsequently the basis for a novel post-Hartree-Fock model of intermolecular interactions[J.Chem.Phys.123,024101(2005)].In the present work,the model is extended to include higher-order dispersion coefficients C_8 and C_(10).The extended model performs very well for prediction of intermonomer separations and binding energies of 45 van der Waals complexes.In particular,it performs twice as well as basis-set extrapolated MP2 theory for dispersion-bound complexes,with minimal computational cost.