title: Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials.
abstract: To tune the efficiency of organic semiconductor devices it is important to understand limiting factors as trapping mechanisms for excitons or charges. An understanding of such mechanisms deserves an accurate description of the involved electronical states in the given environment. In this study, we investigate how a polarizable surrounding influences the relative positions of electronically excited states of dimers of different perylene dyes. Polarization effects are particularly interesting for these systems, because gas phase computations predict that the CT states lie slightly above the corresponding Frenkel states. A polarizable environment may change this energy order because CT states are thought to be more sensitive to a polarizable surrounding than Frenkel states. A first insight we got via a TD-HF approach in combination with a polarizable continuum model (PCM). These give limited insights because TD-HF overestimates excitation energies of CT states. However, SCS-CC2 approaches, which are sufficiently accurate, cannot easily be used in combination with continuum solvent models. Hence, we developed two approaches to combine gas phase SCS-CC2 results with solvent effects based on TD-HF computations. Their accuracies were finally checked via ADC(2)//COSMO computations. The results show that for perylene dyes a polarizable surrounding alone does not influence the energetic ordering of CT and Frenkel states. Variations in the energy order of the states only result from nuclear relaxation effects after the excitation process. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Julius-Maximilians-Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D-97074, Würzburg.
authors.forename: Daniel
authors.initials: D
authors.lastname: Bellinger
authors.affiliation: Julius-Maximilians-Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D-97074, Würzburg.
authors.forename: Volker
authors.initials: V
authors.lastname: Settels
authors.affiliation: Julius-Maximilians-Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D-97074, Würzburg.
authors.forename: Wenlan
authors.initials: W
authors.lastname: Liu
authors.affiliation: Julius-Maximilians-Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D-97074, Würzburg.
authors.forename: Reinhold F
authors.initials: RF
authors.lastname: Fink
authors.affiliation: Julius-Maximilians-Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D-97074, Würzburg.
authors.forename: Bernd
authors.initials: B
authors.lastname: Engels
keywords: COSMO; Frenkel state; IEFPCM; SCS-ADC(2); TD-HF; charge transfer state; excited state; perylene; polarizable surrounding; solvent effect