We present the results of the electronic structure investigation of the active site of [NiFe]-hydrogenase. The energies of the lowest lying singlet and triplet states were calculated with density functional theory and with multireference quasidegenerate perturbation theory. The quasidegeneracy of the lowest lying singlet and triplet electronic states at the distorted square planar geometry suggests a possibility of non-adiabatic multistate reaction mechanism for hydrogen activation. The calculated value of the spin-orbit coupling matrix element supports this hypothesis. We believe that this type of multistate reactivity can play an important role in other reactions catalyzed by transition metal complexes and metalloproteins.

Multistate reaction mechanism of biological hydrogen catalysis

243rd National Meeting (2012)

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