Quantum chemical estimation of the overtone contribution to the IR spectra of hydrocarbon halogen derivatives

Pavlyuchko, A. I.; Vasiliev, E. V.; Грибов, Л. А.

doi:10.1007/s10947-010-0161-5

Cited by 10 publications

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“…The contribution of overtone and combined absorption bands to the overall experimental absorption varied from 1% for difluorodichloromethane to 12% for divinyl with an average of 5%. The nature of the change of this contribution as a function of molecular structure correlated well with the numerical estimation made earlier [7][8][9][10]. A comparison of the calculated and experimental data indicated that the calculation overestimated systematically the absolute intensities of fundamental absorption bands.…”

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Ab initio calculation of band absolute intensities in IR spectra

2012

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539.194.01 Ab initio calculations in a harmonic approximation of absorption band absolute intensities in infrared spectra were carried out for 3 hydrocarbons and 14 halogenated hydrocarbons. The calculated data were compared with experimental values of the absolute absorption intensities. It is shown that a Hartree-Fock calculation method overestimates significantly (by an average of 66%) the integrated absolute intensities of the fundamental bands in the region 575-4000 cm -1 . The deviation is reduced to 32% in the case of the MP2 method of accounting for electron correlations. Most of the overestimation occurs for bands corresponding to vibrations involving halogen atoms.

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