Theoretical investigation of energetics and kinetics of multi-state reactions

为了研究涉及电子态跃迁的多态反应的机理、能量学和动力学，发展了一种基于密度矩阵重整化群（DMRG）理论的多参考电子关联方法.该方法使直接量子建模的多电子波函数的系统，这提供了一个概念上完整的物理描述的系统，是一个具有里程碑意义的挑战，量子化学。随着这些进展，量子化学DMRG已被应用到计算的势能面的CO2裂解的萤火虫荧光素的化学发光，和Mn4CaO5团簇的电子态的光系统II，这一直阻碍了由这些复杂的系统所表现出的多参考波函数的指数复杂性。DMRG计算支持最近对X射线晶体学确定的结构进行的修改，并进一步确定了与X射线畸变相关的多个低能量表面，突出了簇化学中的多态反应性。

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.