Theory of charge-transfer spectra in frozen media

Abstract

Absorption and fluorescence maxima of charge-transfer spectra in frozen media are treated, noting that only some of the nuclear motions for liquid medium are frozen in corresponding solid or glassy phase. Account is taken of the fact that the conditions under which the static dielectric constant of the frozen phase is measured do not usually correspond to those in which the initial state of the solute system is prepared. Expressions for the maxima are obtained in terms of the optical and static dielectric constants of the liquid and frozen (solid or glassy) phases. Comparison of Stokes shifts hv_a-hv_f at conventional fluorescence times in frozen media with Stokes shifts at picosecond or subpicosecond times in liquid media would be of interest.

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