Static and Dynamic Electron Correlation in the Ligand Noninnocent Oxidation of Nickel Dithiolates,The Journal of Physical Chemistry A

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Static and Dynamic Electron Correlation in the Ligand Noninnocent Oxidation of Nickel Dithiolates
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-20 00:00:00 , DOI: 10.1021/acs.jpca.7b09567
Anthony W. Schlimgen ₁ , David A. Mazziotti ₁

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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.

中文翻译：

二硫代镍的配体非纯氧化中的静态和动态电子相关

金属二硫醇盐具有广泛的应用范围，从催化作用到分子导体，在电化学氧化过程中，配体是电子的源，其作用称为配体无毒。钒氧配合物和锰超氧化物歧化酶的最新大规模变分双电子密度降低矩阵（2-RDM）计算表明，量子纠缠稳定了电子向配体的添加，为配位体无毒提供了量子力学解释。在本文中，我们确认并探索了双（乙烯-1,2-二硫代lato）镍或[Ni（edt ₂）] ^{（−2，–1,0）}的电子氧化序列中的配体非纯与变式2-RDM计算。尽管该系列以前的波函数计算仅选择了配体π轨道作为要关联的关键（活性）轨道，但我们发现配体π和镍d轨道都必须关联才能生成电子传递过程的真实图片。。使用计算的2-RDM播种反Hermitian收缩Schrödinger方程的解，我们预测单重态的能量低于三重态的能量，这与实验观察结果一致。

更新日期：2017-11-20

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