σ/σ and π/π Two-center three-electron bonding in complexes formed between charged thiocyanate and X radicals (X=Cl, Br, I and SCN)

Structure, bonding and spectra of various intermediates formed on the reaction of thiocyanate anion (SCN −) with Cl, Br, I and SCN radicals are investigated following ab initio electronic structure theory with 6-311+G(d) set of basis function. Visualization of relevant localized MOs in SCNX − system...

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Bibliographic Details
Published in:Journal of molecular structure. Theochem 2005-11, Vol.755 (1), p.241-245
Main Authors: Pathak, Arup Kumar, Mukherjee, Tulsi, Maity, Dilip Kumar
Format: Article
Language:English
Subjects:
Ab initio
Absorption maximum
DFT
Stretching frequency
Two-center three-electron bond
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Summary:Structure, bonding and spectra of various intermediates formed on the reaction of thiocyanate anion (SCN −) with Cl, Br, I and SCN radicals are investigated following ab initio electronic structure theory with 6-311+G(d) set of basis function. Visualization of relevant localized MOs in SCNX − systems (X=Cl, Br, I and SCN) depicts the presence of a σ type two-center three-electron (2c-3e) bond between two hetero atoms and the optical absorption is assigned to σ→σ* transition. However, dimer radical cation, ( SCN ) 2 · + shows the formation of a π type 2c-3e bond between two hetero atoms and the corresponding optical absorption is assigned to π→π* transition.
ISSN:0166-1280
1872-7999
DOI:10.1016/j.theochem.2005.08.033