A Simple Potential Model Criterion for the Quality of Atomic Charges

Abstract

The simple potential model has been shown to be useful in relating core electron binding energies measured in the X-ray region with mean dipole moment derivatives obtained from experimental infrared vibrational intensities. The importance of including relaxation corrections to the experimental 1s ionization energies of sp, sp2, and sp3 hybridized carbon atoms are investigated here. Although relaxation energies obtained from 6-31G(d,p) and 6-311++G(3df,3p) basis sets using ΔSCF calculations show differences of about 1 eV for most molecules studied, relative differences are of the order of 0.1 eV. Exceptions are the CO, CO2, COS, and CS2 molecules where discrepancies are larger. Relaxation energy corrections improve simple potential model fits with mean dipole moment derivatives for all carbon atom models but is most pronounced for the sp hybridized atoms. The simple potential model corrected for relaxation energies is investigated as a criterion for testing the quality of Mulliken, CHELPG, Bader and GAPT c...