On the Relation Between Core Electron Binding Energies and Atomic Charge

Larsson, Ragnar; Folkesson, Börje; Sadlej, Joanna

doi:10.1080/00387019108018148

Cited by 2 publications

(1 citation statement)

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“…Several workers 1,25,[35][36][37][38][39][40][41] have shown that the potential model of eq 6 is useful for atomic charge analysis. Some of the earlier investigations 1,25,37,38 employed approximate semiempirical or ab initio Hartree-Fock level calculated charges and were unable to identify different models for the hybridized states of the carbon atoms.…”

Section: Discussionmentioning

confidence: 99%

A Simple Potential Model Criterion for the Quality of Atomic Charges

et al. 1999

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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, sp 2 , and sp 3 hybridized carbon atoms are investigated here. Although relaxation energies obtained from 6-31G(d,p) and 6-311++G(3df,3p) basis sets using ∆SCF 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, CO 2 , COS, and CS 2 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.

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