The use of atomic intrinsic polarizabilities in the evaluation of the dispersion energy.
The recent approach presented by Becke and Johnson [J. Chem. Phys. 122, 154104 (2005); 123, 024101 (2005); 123, 154101 (2005); 124, 174104 (2006); 124, 014104 (2006)] for the evaluation of dispersion interactions based on the properties of the exchange-hole dipole moment is combined with a Hirshfeld-type partitioning for the molecular polarizabilities into atomic contributions, recently presented by some of the present authors [A. Krishtal et al., J. Chem. Phys. 125, 034312 (2006)]. The results on a series of nine dimers, involving neon, methane, ethene, acetylene, benzene, and CO(2), taken at their equilibrium geometry, indicate that when the C(6), C(8), and C(10) terms are taken into account, the resulting dispersion energies can be obtained deviating 3% or 8% from high level literature data [E. R. Johnson and A. D. Becke, J. Chem. Phys. 124, 174104 (2006)], without the use of a damping function, the only outlier being the parallel face-to-face benzene dimer.
Olasz
András
A
Department of Inorganic Chemistry, Budapest University of Technology and Economics, Gellért tér 4, H-1521 Budapest, Hungary.
Vanommeslaeghe
Kenno
K
Krishtal
Alisa
A
Veszprémi
Tamás
T
Van Alsenoy
Christian
C
Geerlings
Paul
P
D001704:Biopolymers / Q000737:chemistry*; D003198:Computer Simulation; D004735:Energy Transfer; D008956:Models, Chemical
D001704:Biopolymers