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

✍ Scribed by D. Šatkovskienė; V. Gineitytė

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 565 KB
• Volume: 58
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1996)58:5<453::aid-qua3>3.0.co;2-x

✦ Synopsis

The dependence of the intramolecular charge transfer through the cT-electron systems of substituted hydrocarbons on the spatial arrangement of the X-C, and C,-C, 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-C, 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 electrondonating substituents ( X ) have been considered separately and the dependence of the resulting charge-transfer direction on the properties of substituent has been established.