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The application of the density matrix method for the investigation of the trans ‐effect of heteroatom in σ‐electron systems
Author(s) -
Šatkovskienė D.,
Gineitytė V.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)58:5<453::aid-qua3>3.0.co;2-x
Subject(s) - chemistry , intramolecular force , bond order , electron density , electron transfer , electron , substituent , computational chemistry , heteroatom , atomic orbital , single bond , bond length , crystallography , stereochemistry , physics , quantum mechanics , organic chemistry , alkyl , crystal structure
The dependence of the intramolecular charge transfer through the σ‐electron systems of substituted hydrocarbons on the spatial arrangement of the X(SINGLE BOND)C α and C β (SINGLE BOND)C γ bonds has been studied using the perturbation theory for the one‐electron density matrix (DM). Analytical expressions for the populations of the orbitals pertinent to the cis ‐ and trans ‐bonds with respect to the X(SINGLE BOND)C α bond have been obtained and analyzed. The Hamiltonian matrix elements determining the predominant direction of the above‐defined charge transfer ( cis or trans ) have been revealed. The electron‐accepting and electron‐donating substituents (X) have been considered separately and the dependence of the resulting charge‐transfer direction on the properties of substituent has been established. © 1996 John Wiley & Sons, Inc.