CLASS-IV CHARGE MODELS - A NEW SEMIEMPIRICAL APPROACH IN QUANTUM-CHEMISTRY

We propose a new criterion for defining partial charges on atoms in mo lecules, namely that physical observables calculated from those partia l charges should be as accurate as possible. We also propose a method to obtain such charges based on a mapping from approximate electronic wave functions. The method is illustrated by parameterizing two new ch arge models called AM1-CM1A and PM3-CM1P, based on experimental dipole moments and, respectively, on AM1 and PM3 semiempirical electronic wa ve functions. These charge models yield rms errors of 0.30 and 0.26 D, respectively, in the dipole moments of a set of 195 neutral molecules consisting of 103 molecules containing H, C, N and O, covering variat ions of multiple common organic functional groups, 68 fluorides, chlor ides, bromides and iodides, 15 compounds containing H, C, Si or S, and 9 compounds containing C-S-O or C-N-O linkages. In addition, partial charges computed with this method agree extremely well with high-level ab initio calculations for both neutral compounds and ions. The CM1 c harge models provide a more accurate point charge representation of th e dipole moment than provided by most previously available partial cha rges, and they are far less expensive to compute.