A two-site triplet exciton hopping model: Application to 3P700

A model is presented describing the effect on spin-polarized transient EPR signals caused by incoherent state hopping between two sites. It is shown that the size of the spin state space can be reduced by half to the subspace described by the site-average Hamiltonian and that the dynamics of the system results in a redistribution of the population between its eigenstates. Analytical expressions for the rates of population redistribution and the line shape are derived for the general case in which the back-and-forth rates are unequal. The EPR signals calculated using these expressions are in very good agreement with those obtained by direct numerical solution of the density matrix rate equations. The model is then used to investigate the influence of exciton hopping on triplet state transient EPR spectra. Using the triplet state of the primary donor of Photosystem I as an example, it is shown that the influence of unequal hopping rates becomes more pronounced in the spectrum at longer delay times after the laser flash.