Excess charge delocalization in organic and biological molecules: some theoretical notions

Abstract

Theoretical and computational investigations of the excess charge distribution (ECD) in molecular complexes have attracted considerable attention as ECD is closely related to electronic properties of organic semiconductors, such as the efficiency of photoinduced charge separation in organic solar cells and charge transport in DNA and proteins. In this paper, we analyze the ECD in several representative models on the basis of ab initio and DFT calculations. We consider how changes in the reorganization energy, electronic coupling and charge transfer energy affect the ECD in the systems. In particular, we compare ECD in π stacks of polycyclic aromatic hydrocarbons and DNA nucleobases. While the π interaction between subunits in the systems is similar in both cases, ECD is quite different: the excess charge is found to be completely delocalized over the hydrocarbon stacks but strongly confined to a single nucleobase in DNA stacks. We also discuss the effects of conformational fluctuations on ECD in the stacks. Finally, ECD in amino acids and its dependence on the conformational changes are briefly considered.