Static and Dynamic Electron Correlation in the Ligand Noninnocent Oxidation of Nickel Dithiolates.
Static and Dynamic Electron Correlation in the Ligand Noninnocent Oxidation of Nickel Dithiolates.
复制标题
二硫醇镍配体非无害氧化中的静态和动态电子相关性。
DOI：
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发表时间：
2017
影响因子：
2.9
通讯作者：
D. Mazziotti
中科院分区：
文献类型：
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作者：
A. W. Schlimgen;D. Mazziotti
金属二硫酯具有广泛的应用，从催化到分子导体，在电化学氧化过程中配体是电子的来源，这种效应被称为配体非无罪。最近对钒氧配合物和锰超氧化物歧化酶的大尺度变分双电子降密度矩阵（2-RDM）计算表明，量子纠缠稳定了配体上电子的添加，为配体非无性提供了量子力学解释。本文通过变分2-RDM计算，证实并探讨了双（乙烯-1,2-二硫代）镍或[Ni(edt2)]（- 2,1,0）电子氧化系列中配体的非无罪性。虽然之前的波函数计算只选择了配体π轨道作为相关的临界（活性）轨道，但我们发现配体π和镍d轨道必须相关联才能生成电子转移过程的真实图像。利用计算得到的2-RDM来求解反厄米缩Schrödinger方程，我们预测单重态的能量比三重态低，这与实验观察结果一致。
Metal dithiolates have a wide range of applications from catalysis to molecular conductors with the ligands being the source of electrons during electrochemical oxidation in an effect known as ligand noninnocence. Recent large-scale variational two-electron reduced-density matrix (2-RDM) calculations of the vanadium oxo complex and manganese superoxide dismutase show that quantum entanglement stabilizes the addition of an electron to the ligands, providing a quantum mechanical explanation for ligand noninnocence. In this paper, we confirm and explore the ligand noninnocence in the electron oxidation series of bis(ethylene-1,2-dithiolato)nickel or [Ni(edt2)](-2,-1,0) with variational 2-RDM calculations. While previous wave function calculations of this series have selected only the ligand π orbitals as the critical (active) orbitals to be correlated, we find that both ligand π and nickel d orbitals must be correlated to generate a realistic picture of the electron-transfer process. Using the computed 2-RDM to seed a solution of the anti-Hermitian contracted Schrödinger equation, we predict that the singlet state is lower in energy than the triplet state, which is consistent with experimental observations.