Multicentred QM/QM methods for overlapping model systems

An improved, more general method for performing multicentred integrated QM/QM calculations is presented. The new approach allows the multicentred approximation to be extended to overlapping model systems, removing a significant limitation of the original approach. The usefulness and numerical accuracy of the equations presented are confirmed via some applications to dipole–dipole, charge–dipole and charge–charge complexes. The method performs well for all of these complexes, which range from very weakly to very strongly bound and in which non-additivity effects on interaction energies range from 0.2 to 17kcalmol^?1.