Ab initio study of the force field, geometry and vibrational assignment of urea

Vijay, Amrendra and Sathyanarayana, DN (1993) Ab initio study of the force field, geometry and vibrational assignment of urea. In: Journal of Molecular Structure, 295 . pp. 245-258.

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Abstract

The optimized goemetry and the complete harmonic force field or urea have been calculated at the ab initio Hartree—Fock level using 3–21G as well as 6–31G basis sets. On this basis, a thorough discussion is presented on the previously observed infrared spectra of urea and urea-$d_4$ in an argon matrix. The accuracy of the force constants was tested by calculating the $^{15}N$-isotopic shifts for the vibrational frequencies of urea and urea-$d_4$, and the agreement between the calculated and observed shifts is remarkably good. The calculated force fields are utilized to critically examine the published experimental assignments of urea and some revisions are suggested. Evidence is presented for large frequency shifts in carbonyl and hydrogen-involving vibrations due to intermolecular hydrogen bonding in the solid state. The theoretical geometry and the ab initio force constants of urea are compared with the results of the experimental study. The theoretical infrared and Raman intensities of the normal modes together with qualitative experimental band intensities are presented. The predicted relative intensities compared well qualitatively with experiment for the matrix isolated species.

Item Type:	Journal Article
Publication:	Journal of Molecular Structure
Publisher:	Elsevier
Additional Information:	Copyright of this article belongs to Elsevier.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	09 Aug 2006
Last Modified:	19 Sep 2010 04:30
URI:	http://eprints.iisc.ac.in/id/eprint/8003

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