Journal of Physical Chemistry, Vol.98, No.30, 7270-7273, 1994
Spectral Effects of Exciton Splitting in Statistical Pairs
For fixed intermolecular distances, exciton states of molecular pairs have a range of splittings and oscillator strengths. Correlation of these two quantities reveals that for random angular distributions the lower lying of the pairs of exciton transitions have, on the average, lower oscillator strength. For distributions with steric constraints typical of planar molecules, this effect is enhanced. The implication of these findings for spectra of planar molecules in polar solvents is that close pairs, normally expected to be recognizable by an exciton splitting, actually exhibit a net blue shift, which tends to mask their presence. A numerical example relating to chlorophyll a spectra is presented.