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A comparative study of the energetics, structures, and mechanisms of the HCN H HNC and LiCN <-> LiNC isomerizations

Sreedhara Rao, V and Vijay, Amrendra and Chandra, AK (1996) A comparative study of the energetics, structures, and mechanisms of the HCN H HNC and LiCN <-> LiNC isomerizations. In: Canadian Journal Of Chemistry-Revue Canadienne De Chimie, 74 (06). pp. 1072-1077.

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Abstract

The potential energy surfaces of the HCN<->HNC and LiCN<->LiNC isomerization processes were determined by ab initio theory using fully optimized triple-zeta double polarization types of basis sets. Both the MP2 corrections and the QCISD level of calculations were performed to correct for the electron correlation. Results show that electron correlation has a considerable influence on the energetics and structures. Analysis of the intramolecular bond rearrangement processes reveals that, in both cases, H (or Li+) migrates in an almost elliptic path in the plane of the molecule. In HCN<->HNC, the migrating hydrogen interacts with the in-plane pi,pi* orbitals of CN, leading to a decrease in the C-N bond order. In LiCN<->LiNC, Li+ does not interact with the corresponding pi,pi* orbitals of CN.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to NRC Research Press.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 28 May 2009 10:55
Last Modified: 19 Sep 2010 05:30
URI: http://eprints.iisc.ernet.in/id/eprint/19865

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