Spherical atom model for dispersion forces

CHED 237

Mi Kyung Lee, mlee03@wesleyan.edu and George A. Petersson, gpetersson@wesleyan.edu. Chemistry Department, Wesleyan University, Hall-Atwater Laboratories of Chemistry, Middletown, CT 06459-0180

A major shortcoming of the local density approximaton (LDA) and generalized gradient approximation (GGA) density functionals (with and without “exact exchange”) is their failure to properly describe long range correlation effects, such as dispersion forces. We present a novel atom-atom pairwise potential function for describing dispersion forces based the interaction of two spherical shells (of radius rs) of polarizable media. The primary deviation from the C6/R6 interaction of two point dipoles is due to the fact that atoms have volume. We will show that the resulting spherical atom potential: , is more accurate for describing dispersion interactions than either damped (radius rd) or undamped C6/R6 potentials, while not significantly affecting the computational cost of DFT methods. The spherical atom model for dispersion forces can also be incorporated into molecular mechanics force fields.