Exchange-hole dipole moment and the dispersion interaction.

A simple model is presented in which the instantaneous dipole moment of the exchange hole is used to generate a dispersion interaction between nonoverlapping systems. The model is easy to implement, requiring no electron correlation (in the usual sense) or time dependence, and has been tested on various atomic and molecular pairs. The resulting C6 dispersion coefficients are remarkably accurate.

[1]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[2]  Evert Jan Baerends,et al.  A density-functional theory study of frequency-dependent polarizabilities and Van der Waals dispersion coefficients for polyatomic molecules , 1995 .

[3]  D. Langreth,et al.  Van Der Waals Interactions In Density Functional Theory , 2007 .

[4]  David J. Tozer,et al.  Helium dimer dispersion forces and correlation potentials in density functional theory. , 2002 .

[5]  J. C. Slater.  A Simplification of the Hartree-Fock Method , 1951 .

[6]  M. Spackman.  Time‐dependent Hartree–Fock second‐order molecular properties with a moderately sized basis set. II. Dispersion coefficients , 1991 .

[7]  Axel D. Becke,et al.  Numerical solution of Schrödinger’s equation in polyatomic molecules , 1990 .

[8]  G. Mahan.  van der Waals coefficient between closed shell ions , 1982 .

[9]  John C. Slater,et al.  The self-consistent field for molecules and solids , 1974 .

[10]  A. Becke.  A multicenter numerical integration scheme for polyatomic molecules , 1988 .

[11]  J. M. Norbeck,et al.  Upper and lower bounds of two‐ and three‐body dipole, quadrupole, and octupole van der Waals coefficients for hydrogen, noble gas, and alkali atom interactions , 1976 .

[12]  P. Atkins,et al.  Molecular Quantum Mechanics , 1970 .

[13]  Fernando Pirani,et al.  Generalized correlations in terms of polarizability for van der Waals interaction potential parameter calculations , 1991 .

[14]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[15]  Qin Wu,et al.  Empirical correction to density functional theory for van der Waals interactions , 2002 .

[16]  Stanton.  Calculation of C6 dispersion constants with coupled-cluster theory. , 1994, Physical review. A, Atomic, molecular, and optical physics.

[17]  Darrin M. York,et al.  High-level ab initio methods for calculation of potential energy surfaces of van der Waals complexes , 2004 .