Intermediate vibronic coupling in charge transfer states: Comprehensive calculation of electronic excitations in sexithiophene crystal

摘要: A comprehensive theory of linear vibronic coupling in a coupled manifold Frenkel and charge-transfer states an infinite molecular crystal is presented applied for sexithiophene. The approach, valid the intermediate-coupling regime, includes up to three-particle terms Philpott expansion, with wavefunctions represented Lang-Firsov basis. As stringent test, scheme used reproduce complete set available sexithiophene absorption electroabsorption spectra within unified theoretical framework. input based primarily on independent calculations some extent experiments, explicit fitting contained limits by estimated inherent errors priori parameter estimates. Reasonably good quantitative agreement experimental achieved. results resolve existing interpretational ambiguities expose peculiarities electric field effect eigenstates parentage, highlighting role interactions.