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Type: Artigo de periódico
Title: ChelpG and QTAIM atomic charge and dipole models for the infrared fundamental intensities of the fluorochloromethanes
Author: Gomes, TCF
da Silva, JV
Vidal, LN
Vazquez, PAM
Bruns, RE
Abstract: ChelpG atomic charges and dipoles and the charge-charge flux-dipole flux (CCFDF) model have been used to quantitatively estimate the fundamental infrared intensities of the fluorochloromethanes. Since the ChelpG calculational procedure includes the constraint that the atomic charges and dipoles reproduce the equilibrium dipole moments the model results in accurate intensity values that have a root mean square error of 0.7 km mol(-1) compared to those determined directly from the MP2/6-311G++(3d,3p) electronic density and 23.1 km mol(-1) relative to the experimental intensities. Although these ChelpG results for total dipole moment derivatives are almost the same as those obtained previously using QTAIM (Quantum Theory of Atoms in Molecules) atomic charges and dipoles in the CCFDF model, their charge, charge flux and dipole flux contributions are completely different. Whereas the contributions calculated using the QTAIM parameters have values following expectations based on electronegativity concepts this is not true for those obtained from the ChelpG parameters. Mean dipole moment derivatives determined from experimental fundamental infrared intensities are compared with the ChelpG and QTAIM atomic charges. Furthermore, Generalized Atomic Polar Tensor Charges (GAPT) are found to need correction for their dynamic contributions if they are to be used as static atomic charges.
Subject: infrared intensities
dipole moment derivatives
atomic charges
Country: EUA
Editor: Springer
Citation: Theoretical Chemistry Accounts. Springer, v. 121, n. 41732, n. 173, n. 179, 2008.
Rights: fechado
Identifier DOI: 10.1007/s00214-008-0461-4
Date Issue: 2008
Appears in Collections:Unicamp - Artigos e Outros Documentos

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