Time resolved emission spectra of Cr(III) pentammine complexes excited at resonance conditions are recorded yielding different lifetimes for zero-phonon and vibronic transitions from B-2(1)(C-4 upsilon) The decay of zero-phonon transitions furthermore depends on the excitation frequency. The energy dependence is rationalized assuming a model which describes energy transfer rates between electronic levels of molecules on equivalent sites which compete with intramolecular rates for the decay into the ground states. Corresponding rate equations worked out for some special cases are shown to have analytical solutions. For a continuous set of excited levels, a differential equation is obtained which is known from diffusion or transport phenomena but contain the energy as variable. Simulation of the experiments leads to transfer rate parameters k(d) which are 1 (or 2) orders of magnitude larger than the decay rate k(0). (C) 1997 American Institute of Physics.