화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.98, No.50, 13418-13425, 1994
A Theory of Dispersive Kinetics in the Energy-Transfer of Antenna Complexes
The inherent glasslike structural heterogeneity of photosynthetic antenna protein complexes is now known to result in a distribution of values for any given donor-acceptor energy gap. The width of the distribution is sufficiently broad to raise the possibility that the kinetics of D-A energy transfer might be dispersive and strongly dependent on temperature especially since the chlorophyll optical transitions are characterized by weak electron-phonon coupling. An approximate theory is presented that allows far computationally simple analysis of this problem. It is based on the familiar nonadiabatric energy-transfer theory and Condon approximation and, thus, is applicable to conventional Forster transfer involving localized phonons. The case of delocalized phonons is also treated. Calculations are presented for a model D-A system which, based on hole-burning data, can be considered to be realistic and typical of many complexes. The results reveal pronounced and temperature-dependent dispersion in the kinetics. The effect of pure electronic dephasing on the calculated results is considered. The theory is not applicable to the situation where excitonic level splittings are large relative to the pure dephasing frequencies of the levels. i.e., where one has to go beyond the Condon approximation. Nevertheless. the theory can be easily extended to cover this strong coupling case which can be expected to be important for many photosynthetic complexes at sufficiently low temperatures. The possibility that strong coupling might lead to a diminuation in the degree of dispersive kinetics is considered.