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Quantum theory of atoms in molecules charge-charge flux-dipole flux models for the infrared intensities of XCY (X = H, F, Cl; y = Q, S) molecules

Journal of Physical Chemistry A, ISSN: 1089-5639, Vol: 111, Issue: 32, Page: 7870-7875
2007
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Article Description

The molecular dipole moments, their derivatives, and the fundamental IR intensities of the XCY (X = H, F, Cl; Y = O, S) molecules are determined from QTAIM atomic charges and dipoles and their fluxes at the MP2/6-311++G(3d,3p) level. Root-mean-square errors of ±0.03 D and ±1.4 km mol are found for the molecular dipole moments and fundamental IR intensities calculated using quantum theory of atoms in molecules (QTAIM) parameters when compared with those obtained directly from the MP2/6-311++G(3d,3p) calculations and ±0.05 D and 51.2 km mol when compared with the experimental values. Charge (C), charge flux (CF), and dipole flux (DF) contributions are reported for all the normal vibrations of these molecules. A large negative correlation coefficient of -0.83 is calculated between the charge flux and dipole flux contributions and indicates that electronic charge transfer from one side of the molecule to the other during vibrations is accompanied by a relaxation effect with electron density polarization in the opposite direction. The characteristic substituent effect that has been observed for experimental infrared intensity parameters and core electron ionization energies has been applied to the CCFDF/QTAIM parameters of FCO, ClCO, FCS, and ClCS. The individual atomic charge, atomic charge flux, and atomic dipole flux contributions are seen to obey the characteristic substituent effect equation just as accurately as the total dipole moment derivative. The CH, CF, and CCl stretching normal modes of these molecules are shown to have characteristic sets of charge, charge flux, and dipole flux contributions. © 2007 American Chemical Society.

Bibliographic Details

Sergio H. D. M. Faria; João Viçozo da Silva; Roberto L. A. Haiduke; Luciano N. Vidal; Pedro A. M. Vazquez; Roy E. Bruns

American Chemical Society (ACS)

Chemistry

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