Energy of Excimer Luminescence. II. Configuration Interaction between Molecular Exciton States and Charge Resonance States

Abstract

A four‐electron MO treatment of the interaction of the D_2h polyacenes naphthalene, anthracene, pyrene, and perylene to yield D_2h dimers is developed, and the energies of these dimers are calculated as functions of the effective nuclear charge to be used in a Slater orbital exponent, and of the intermolecular distance D. Agreement with excimer luminescence energies is obtained for values of Z∼3 and values of D between 3.0 and 3.6 Å. Contact absorption processes are predicted to occur and are discussed. An Appendix which provides simple analytic expressions for four different types of penetration integrals is included.