Construction of molecular mechanics energy functions by mathematical transformation of ab initio force fields and structures

Abstract

A method is presented by which ab initio (or empirical) force fields and structures can be converted to molecular mechanics energy parameters. Using Cartesian coordinates, the effect of van der Waals and other nonquadratic interactions is eliminated from the original spectroscopic force field, and molecular mechanics force constants and reference geometry parameters are derived. The computed parameters yield molecular structure and vibrational frequencies that are identical to the original ones. The transformation produces a complete general valence force field, which in most cases is impractical, and a procedure to reduce the number of force constants is therefore described. Different ways of applying the transformation are outlined.