Atomic polarizations necessary for coherent infrared intensity modeling with theoretical calculations.

Abstract

The inclusion of atomic polarizations for describing molecular electronic structure changes on vibration is shown to be necessary for coherent infrared intensity modeling. Atomic charges from the ChelpG partition scheme and atomic charges and dipoles from Quantum Theory of Atoms in Molecules (QTAIM) were employed within two different models to describe the stretching and bending vibrational intensities of the C-H, C-F, and C=O groups. The model employing the QTAIM parameters was the Charge-Charge Transfer and Dipolar Polarization model (QTAIM/CCTDP), and the model employing the ChelpG charges was the Equilibrium Charge-Charge Flux (ChelpG/ECCF). The QTAIM/CCTDP models result in characteristic proportions of the charge-charge transfer-dipolar polarization contributions even though their sums giving the total intensities do not discriminate between these vibrations. According to the QTAIM/CCTDP model, the carbon monoxide intensity has electronic structure changes similar to those of the carbonyl stretches whereas they resemble those of the CH stretches for the ChelpG/ECCF model.