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

Abstract

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.

A Systematic CCSD(T) Study of Long-Range and Noncovalent Interactions between Benzene and a Series of First- and Second-Row Hydrides and Rare Gas Atoms

“…Although approximate methods for describing these interactions have long been utilized in molecular mechanics and molecular dynamics simulations, 1 it is only recently that the development of more accurate models has become the focus of the density functional theory (DFT) community. [2][3][4][5][6][7][8][9] However, the development of accurate models requires high-quality benchmark data for calibration and comparison, and a number of authors have noted that very few high-quality potential energy curves are available for prototype noncovalent interactions. 2,10 In particular, Grimme has recently noted that very accurate ab initio data are still missing for complexes of benzene with small molecules.…”

Intra‐ and Intermolecular Dispersion Interactions in [n]Cycloparaphenylenes: Do They Influence Their Structural and Electronic Properties?

“…and a 1 (2) fitted parameters for the functionals used here [44][45][46]. Note that the older -D2 correction [47,48] is a simplification (a first-version) of the above approach, which is however widely and successfully used too.…”

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

“…204 Two distinct damping functions were suggested for XDM. 195,203 The first one uses an approach based on correlation energy ratios,…”

“…The approach was also extended to include higher-order C n coefficients and modified so that the dependence on the static molecular polarizability as an external input was removed. 194 Finally, all of these incremental improvements were combined into a single general pairwise method for vdW interactions in ref 195.…”