Theoretical investigation of energetics and kinetics of multi-state reactions

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To investigate mechanisms, energetics, and kinetics of multi-state reactions that involves electronic state transitions, an efficient multi-reference electron correlation method that is based on the density matrix renormalization group (DMRG) theory has been developed. The method enables the direct quantum modeling of the many-electron wavefunction of such systems, which provides a conceptually complete physical description of the system, is a landmark challenge of quantum chemistry. With these advances, the quantum-chemical DMRG has been applied to the calculation for the potential energy surface of the CO2 cleavage in the chemiluminescence of the firefly luciferin, and the electronic state of the Mn4CaO5 cluster in the photosystem II, which had been hampered by the exponential complexity of the multireference wavefunctions exhibited by these complex systems. The DMRG calculations support recent modifications to the structure determined by X-ray crystallography, and further identify multiple low-lying energy surfaces associated with the X-ray distortion, highlighting multi-state reactivity in the chemistry of the cluster.