A new algorithm for molecular fragmentation in quantum chemical calculations

Abstract

In this study, we present a "black-box" method for fragmenting a molecule with a well-defined Kekulé or valence-bond structure into a significant number of smaller fragment molecules that are more amenable to high level quantum chemical calculations. By taking an appropriate linear combination of the fragment energies, we show that it is possible in many cases to obtain highly accurate total energies when compared to the total energy of the full molecule. Our method is derived from the approach reported by Deev and Collins,43 but it contains significant unique elements, including an isodesmic approach to the fragmentation process. Using a method such as that described in this work it is in principle possible to obtain very accurate total energies of systems containing hundreds, if not thousands, of atoms as the approach is subject to massive parallelization. © 2006 American Chemical Society.