Artículos de revistas
Quantum Theory Atoms in Molecules Charge-Charge Flux-Dipole Flux Models for the Infrared Intensities of Benzene and Hexafluorobenzene
Registro en:
Journal Of Physical Chemistry A. Amer Chemical Soc, v. 113, n. 27, n. 7972, n. 7978, 2009.
1089-5639
WOS:000267694800035
10.1021/jp903255e
Autor
da Silva, JV
Oliveira, AE
Hase, Y
Bruns, RE
Institución
Resumen
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The infrared fundamental intensities of benzene and hexafluorobenzene have been calculated at the MP2/6-311 ++G(3d,3p) level. The theoretical values are in excellent agreement with the averaged experimental C(6)H(6) results having a rms error of 15.3 km mol(-1). However, the theory badly underestimates the CIF stretching and ring deformation intensities Of C(6)F(6) having an overall rms error of 141 km mol(-1). The theoretical results confirm the dipole moment derivative signs previously attributed on the basis of the comparison Of C6H6 and C(6)D(6) derivatives and semiempirical Molecular orbital results. A quantum theory atoms in molecules charge-charge flux-dipole flux interpretation of the theoretical results shows that electronic density changes for out-of-plane vibrations can be explained using a simple bond moment-rehybridization moment model proposed many years ago. However, these changes were found to be much more complicated for the in-plane vibrations involving important charge flux and dipole flux contributions for both molecules as well as contributions from the displacement of equilibrium atomic charges for hexafluorobenzene. 113 27 7972 7978 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)