Simplified schematic diagram of the states and pathways of formation following photolysis of AdoCbl in solution and in holo-EAL. The cobalt in cobalamin and the C5′-methylene center in the 5′-deoxyadenosyl moiety are represented, as follows: [CoIII-C], intact coenzyme; [CoIII-C]*, excited singlet state; [CoII •C]gem, geminate radical pair; CoII •C, cage escaped radical pair. Intermediate excited and relaxed states,27,32 which are not shown, are represented by the sequence of arrows leading from [CoIII-C]*. Rate constants are defined as follows: kr, excited state to ground state relaxation; kgr, geminate recombination; kce, cage escape; kcer, reformation of geminate radical pair from cage escaped radical pair. The subscript, i, refers to three different cage escaped photoproduct radical pair species, Pi, that were identified in holo-EAL.26