Vibronic exciton interactions. Resolution and interpretation of the temperature-dependent circular dichroism and absorption spectra of ApA and of dApdA

The circular dichroism and absorption spectra of the stacked and unstacked forms of ApA and dApdA were derived. The unstacked spectra are not identical with the corresponding free nucleoside spectrum. The stacked spectra can be satisfactorily described in terms of the vibronic degenerate exciton theory which suggests that the non-degenerate interactions have a less important influence on the observed circular dichroic spectra than hitherto assumed. From the experimental spectra the magnitudes of the exciton coupling were found to correspond to very fast transfer rates of energy between the adenine moieties. The absorption spectra of the stacked species are consistent with average angles of near 60 degrees and 20 degrees in ApA and dApdA, respectively, between the degenerate transition moments of the adenine moieties.