Dipole Davydov Splittings in Crystalline Anthracene, Tetracene, Naphthalene, and Phenanthrene

摘要: The contribution of dipole–dipole interactions to the Davydov splitting (i.e., dipole splitting) moderately intense 1Ag → 1La transitions anthracene, tetracene, naphthalene, and phenanthrene has been investigated. Unlike most previous calculations, Bose character molecular excitons taken fully into account by using classical theory exciton states. In approximation this treatment is equivalent second quantized formulation Agranovitch. Formulas are also derived for coupling Born–Oppenheimer separable states through full interaction potential. Dipole sums calculated infinite crystals Ewald's method. High‐energy π–π* shown make sizeable contributions splittings responsible increasing polarization ratios 0–0 transition. For anthracene these high‐energy push 3800‐A system beyond accepted values, implying that residual intermolecular interac...