A Simple Potential Model Criterion for the Quality of Atomic Charges

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 103; no. 25; pp. 4918 - 4924
• Main Authors: de Oliveira, Anselmo E, Guadagnini, Paulo H, Haiduke, Roberto L. A, Bruns, Roy E
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.06.1999
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp984777e

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 carbon atomic charges calculated from MP2/6-311++G(3d,3p) wave functions. The GAPT charges are in excellent agreement with the experimental mean dipole moment derivatives (within 0.067e) and provide superior statistical fits to the simple potential model when compared with those obtained for the other charges.