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Quantification of intramolecular nonbonding interactions in organochalcogens

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Title Quantification of intramolecular nonbonding interactions in organochalcogens
 
Creator ROY, D
SUNOJ, RB
 
Subject correlated molecular calculations
density-functional theory
ab-initio calculations
gaussian-basis sets
center-dot-o
glutathione-peroxidase
hydrogen-bonds
nmr-spectroscopy
charge-density
se-77 nmr
 
Description Intramolecular nonbonding interactions between chalcogen atoms in a series of ortho substituted arylselenides (S/O center dot center dot center dot Se- Y, with Y = -Me, -CN, -Cl, and -F) are quantified using the coupled cluster CCSD(T)/cc-pVDZ level of theory. A homodesmic reaction method as well as an ortho-para approach are employed in evaluating the strength of intramolecular interactions. Comparison of the results obtained using the ab initio MP2 method and pure and hybrid density functional theories are performed with that of the coupled cluster values to assess the quality of different density functionals in evaluating the strength of nonbonding interactions. The interaction energies are found to be higher when the thioformyl group acts as the donor and the Se-F bond acts as the acceptor. In a given series with the same donor atom, the strength of the interaction follows the order Me < CN < Cl < F, exhibiting fairly high sensitivity to the group attached to selenium (Se-Y). Analysis of electron density at the S/O center dot center dot center dot Se bond critical point within the Atoms in Molecule framework shows a very good correlation with the computed intramolecular interaction energies.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T17:17:46Z
2011-12-26T12:49:05Z
2011-12-27T05:34:47Z
2011-07-14T17:17:46Z
2011-12-26T12:49:05Z
2011-12-27T05:34:47Z
2006
 
Type Article
 
Identifier JOURNAL OF PHYSICAL CHEMISTRY A, 110(17), 5942-5947
1089-5639
http://dx.doi.org/10.1021/jp060218t
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4020
http://hdl.handle.net/10054/4020
 
Language en