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. (c) 2006 American Institute of Physics.