Rate constants for photochemical charge separation and recombination in a zinc-porphyrin-benzoquinone cyclophane are calculated by an approach that was developed recently to include effects of vibrational dephasing and relaxation and to reduce the dependence on freely adjustable parameters. The theory is extended to treat the rate of vibrational relaxation individually for each vibrational sublevel of the initial charge-transfer product. Quantum-mechanical/molecular-mechanical simulations of the reactions in iso-octane, toluene, dichloromethane, and acetonitrile suggest that charge separation occurs at conical intersections in the two more polar solvents, but at avoided crossings in the nonpolar solvents. In agreement with experimental measurements, however, the calculated rate constants for charge separation are similar in polar and nonpolar solvents. Charge recombination to the ground state is found to have electronic coupling factors smaller than that of charge separation and to be affected more strongly by interactions with the solvent.