Johnson Erin R, Becke Axel D
Department of Chemistry, Queen's University, Kingston, Ontario, Canada.
J Chem Phys. 2006 May 7;124(17):174104. doi: 10.1063/1.2190220.
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.
我们之前已经证明，交换空穴的偶极矩可用于推导分子间的C(6)色散系数[《化学物理杂志》122, 154104 (2005)]。这随后成为了一种新型分子间相互作用后哈特里 - 福克模型的基础[《化学物理杂志》123, 024101 (2005)]。在当前工作中，该模型被扩展以纳入高阶色散系数C(8)和C(10)。扩展后的模型在预测45个范德华复合物的单体间分离和结合能方面表现出色。特别是，对于色散束缚复合物，它的表现比基组外推的MP2理论好两倍，且计算成本极低。
