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The lifetime of the MLCT state is inversely related to the size of the alkyl ligand: 1 ns (methyl), 48 ps (ethyl), 32 ps (n-propyl), and 14 ps (adenosyl, if the MLCT state is present).Excitation at 400 nm opens a pathway for direct photohomolysis of the carbon-cobalt bond in methyl-, ethyl-, and n-propylcobalamin