Ultrafast Cascading Theory in Intersystem Crossings in Transition-Metal Complexes

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We investigate the cascade decay mechanism for ultrafast intersystem crossing mediated by the spin-orbit coupling in transition-metal complexes. A quantum-mechanical description of the cascading process that occurs after photoexcitation is presented. The conditions for ultrafast cascading are given, which relate the energy difference between the levels in the cascading process to the electron-phonon self energy. These limitations aid in the determination of the cascade path. For Fe²⁺ spin-crossover complexes, this leads to the conclusion that the ultrafast decay primarily occurs in the manifold of antibonding metal-to-ligand charge-transfer states. We also give an interpretation why some intermediate states are bypassed.