Intermolecular potentials with flexible monomers

Abstract

Most available intermolecular potentials assume rigid monomers. Such an assumption is a reflection of a trivial observation that if monomer degrees of freedom are considered, the dimensionality of an intermolecular potential increases dramatically even for few-atom monomers. This puts strict limits on the sizes of clusters with flexible monomers that can be treated by ab initio methods since the number of grid points needed to fit a potential surface quickly becomes enormous. Most of the literature flexible-monomer potentials were obtained from the so-called site–site rigid-monomer potentials by simply allowing the sites to move with atomic nuclei as the monomers are deformed. This simple atom-following approach has been investigated in the present work, using water dimer and Ar–HF as test systems, and shown to be not adequate. A method has been proposed which uses properties of isolated flexible monomers to improve upon the atom-following approach without performing any dimer calculations outside the rigid-monomer grid. The method is shown to give for Ar–HF a 3D representation of the dispersion energy that should be adequate for HF motion in the ground and first excited vibrational states.