Orbital symmetry and concerted reactions in terms of exact wavefunctions

✍ Scribed by E. Bright Wilson; P.S.C. Wang

• Publisher: Elsevier Science
• Year: 1972
• Tongue: English
• Weight: 314 KB
• Volume: 15
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(72)80199-4

✦ Synopsis

Correlation diagrams using orbital symmetry analogous to those of Woodward and Hoffmann for classifying concerted chemical reactions can be drawn for csacr wavefunctions.

The occupation numbers of the natural orbit& will normally show crossing between orbitals of high and of low occupation number for typical "forbidden" reactions and no such crossing for "allowed" reactions. Although not now adding any new predictive power, this picture provides the rules with a basis in terms of wavefunctions with exchange, correlation energy, and orbit& depending on OCCUpanty, instead of the approximations of simple MO theory.

The Woodward-Hoffmann rules [ 1, 2] ff for concerted reactions are usudly expressed in terms of