The application of the density matrix method for the investigation of the trans-effect of heteroatom in σ-electron systems

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.