title: Applicability of the SQM force field method to the vibrational spectra of sodium acetate.
abstract: The applicability of the scaled quantum mechanical force field (SQM FF) method to the prediction of the vibrational spectra of a charged molecule has been studied by the example of the acetate ion (CH3CO2-) in sodium acetate for which an efficient empirical valence force field (SVFF) based on observed IR spectra of six isotopomers of sodium acetate is available in the literature. Standard SQM FF calculations done on a free acetate ion at the B3LYP/6-31G level failed to give an acceptable estimation of even the most characteristic features of the observed spectra, which can be exemplified by the gross overestimation of the frequency separation of the nu(a)CO2- and nu(s)CO2- vibrations. In search for a better description, SQM calculations were done for three simple structural models of sodium acetate, testing different QM methods. The results indicate that in addition to taking into account the dielectric field effect of the surrounding medium, incorporation of a Na+ counterion is necessary to achieve a realistic simulation of the IR and Raman spectra. Satisfactory results were obtained with a bidentate Na-acetate complex by the SQM method coupled with a continuum model at the B3LYP/6-31+G level, whereas the use of the Onsager-type spherical cavity model and the polarizable continuum model (PCM) were found preferable over SCI-PCM.
authors.affiliation: Chemical Research Center, Hungarian Academy of Sciences, P.O. Box 17, H-1525 Budapest, Hungary. kergabor@chemres.hu
authors.forename: Gabor
authors.initials: G
authors.lastname: Keresztury
authors.forename: Krisztina
authors.initials: K
authors.lastname: Istvan
authors.forename: Tom
authors.initials: T
authors.lastname: Sundius