Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions

Rao, Sreedhara V and Sengupta, Debasis and Chandra, AK (1996) Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions. In: Journal of Molecular Structure (Theochem), 361 (1-3). pp. 151-160.

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Abstract

The principle of the conservation of bond orders during radical-exchange reactions is examined using Mayer's definition of bond orders. This simple intuitive approximation is not valid in a quantitative sense. Ab initio results reveal that free valences (or spin densities) develop on the migrating atom during reactions. For several examples of hydrogen-transfer reactions, the sum of the reaction coordinate bond orders in the transition state was found to be 0.92 +/- 0.04 instead of the theoretical 1.00 because free valences (or spin densities) develop on the migrating atom during reactions. It is shown that free valence is almost equal to the square of the spin density on the migrating hydrogen atom and the maxima in the free valence (or spin density) profiles coincide (or nearly coincide) with the saddle points in the corresponding energy profiles.

Item Type:	Journal Article
Publication:	Journal of Molecular Structure (Theochem)
Publisher:	Elsevier Science
Additional Information:	Copyright of this article belongs to Elsevier Science.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	13 May 2011 10:30
Last Modified:	13 May 2011 10:30
URI:	http://eprints.iisc.ac.in/id/eprint/37518

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