Abstract
Abstract The local or extended nature of molecular ion or exciton states in molecular solids is determined by a competition between fluctuations in the local site energies of these states (which tend to localize them) and the hopping integrals for inter-site excitation transfer (which tend to delocalize them). This paper constitutes a brief survey of a body of work in which the parameters governing the localization of molecular ion states are evaluated spectroscopically with the aid of molecular orbital theory and subsequently utilized to assess the character of these states in a variety of molecular solids, including pendant-group polymers, Van der Waals crystals, and segregatedstack, quasi-onedimensional charge transfer salts. To illustrate the utility of this approach the example of electron localization in polystyrene (PS) and poly(2-vinyl pyridine)(PVP) is developed. Specifically, a model of electron interactions with longitudinal polarization fluctuations is described and shown to predict the (relax...
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