Intermolecular correlation in a new approximation scheme

✍ Scribed by S. Aronowitz

• Publisher: John Wiley and Sons
• Year: 1978
• Tongue: English
• Weight: 898 KB
• Volume: 14
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560140305

✦ Synopsis

Abstract

It is demonstrated for a spin‐free, nonrelativistic, complete molecular Hamiltonian that there is an optimal solution to the separation of electronic and nuclear motions. The adiabatic approximation is obtained as a special limiting case. A fruitful interpretation of intermolecular correlation results from the assumption that such correlation involves the degeneracy of a molecular‐energy state of one molecule with that of another chemical species, e.g., cubane and cyclooctatetraene. As a consequence, rigorous relationships are established for the influence of nodal patterns of the electronic functions on intermolecular correlation. Also derived are stringent symmetry rules which both electronic and nuclear functions involved in the correlation must obey. Throughout the treatment is a many‐electron one.