Excited state trapping and the Stepanov relation with reference to Photosystem I

It has been previously demonstrated that the Stepanov equation provides a rather good description of the absorption/fluorescence spectra in Photosystem I, even though excited state equilibration is not rapid with respect to the excited state decay. In the present article this apparent contradiction is examined analytically for two-state systems and numerically for many-state systems. It is demonstrated that, in the special case of the trapping process being associated with the initially populated state, neither very rapid excited state equilibration nor a transfer equilibrium, which approximates a true Boltzmann distribution, are prerequisites to obtaining a very close approximation to a correct Stepanov result. This interesting conclusion is discussed in terms of plant Photosystem I (PSI-200). It is concluded that whereas, in compartmental modeling, photochemical trapping may be formally associated with the bulk antenna pigments due to the strong energy coupling between them and the trap pigments, this is not the case for the red spectral forms.