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The molecular dipole moment and its derivatives are determined from atomic charges, atomic dipoles, and their fluxes obtained from AIM formalism and calculated at the MP2(FC)/6-311++G(3d,3p) level for 16 molecules: 6 diatomic hydrides, CO, HCN, OCS, CO2, CS2, C2H2, C2N2, H2O, H2CO, and CH4. Root-mean-square (rms) errors of 0.052 D and 0.019 e are found for the dipole moments and their derivatives calculated using AIM parameters when compared with those obtained directly from the MP2(FC)/6-311++G(3d,3p) calculations and 0.097 D and 0.049 e when compared to the experimental values. The major deviations occur for the NaH, HF, and H2O molecules. Parallel polar tensor elements for the diatomic and linear polyatomic molecules, except H2, HF, LiH, and NaH, have values resulting from cancellations of substantial contributions from atomic charge fluxes and atomic dipole fluxes. These fluxes have a large negative correlation coefficient, -0.97. IR fundamental intensity sums for CO, HCN, OCS, CO2, CS2, C2H2, C2N2, H2CO, and CH4 calculated using AIM charges, charge fluxes, and atomic dipole fluxes have rms errors of 14.9 km mol(-1) when compared with sums calculated directly from the molecular wave function and 36.2 km mol(-1) relative to experimental values. The classical model proposed here to calculate dipole-moment derivatives is compared with the charge-charge flux-overlap model long used by spectroscopists for interpreting IR vibrational intensities. The utility of the AIM atomic charges and dipoles was illustrated by calculating the forces exerted on molecules by a charged particle. AIM quantities were able to reproduce forces due to a +0.1 e particle over a 3-8-A separation range for the CO and HF molecules in collinear and perpendicular arrangements. These results show that IR intensities do contain information relevant to the study of intermolecular interactions.

Carbon 1s electron binding energies determined by X-ray photoelectron spectroscopy and mean dipole moment derivatives obtained from experimental infrared intensities are shown to be related through the simple potential model proposed by Siegbahn and collaborators. The sp3 carbon atoms in 13 halomethanes, 2 ethanes, 3 methylacetylenes, cyclopropane, and ethylene oxide have 1s energies, which, after correction for electrostatic potentials from neighboring atoms, are linearly related to the carbon mean dipole moment derivatives, presenting a slope of 15.50 ± 0.29 eV/e. The sp2 carbons of ethylene, three haloethylenes, and three carbonyl compounds also exhibit a linear relationship having a significantly different slope of 17.37 ± 0.87 eV/e. The sp carbon atoms in acetylenes, cyanides, CO, CS2, CO2, and OCS show a third linear relationship, with a slope of 18.90 ± 0.75 eV/e. These slopes are proportional to the inverse atomic radii of sp3, sp2, and sp carbon atoms and according to the simple potential equation can be interpreted as estimates of Coulomb repulsion integrals involving these hybridized orbitals and the 1s core electron orbitals. Two basic assumptions of the potential model are investigated. The effect of relaxation energies on the 1s electron ionization processes is estimated as the difference between ΔSCF ionization energies and Koopmans' frozen orbital estimates obtained from 6-31G(d,p) wave functions. These results are compared with values obtained previously from the equivalent cores estimating procedure. Also the conceptual validity of identifying the carbon mean dipole moment derivatives as atomic charges is discussed within the framework of the charge−charge flux-overlap model.