过渡金属配合物绝热势能面有效取样的Anderson杂质模型
An Anderson Impurity Model for Efficient Sampling of Adiabatic Potential Energy Surfaces of Transition Metal Complexes
摘要：
我们提出了一个模型，旨在快速采样的第一行过渡金属活性位点的基态和激发态势能面。该方法计算成本低，适合于动力学模拟，其中（1）绝热状态需要“即时”和（2）非绝热状态之间的电子耦合的主要来源是3d电子之间的微扰自旋轨道相互作用。我们开发的模型哈密顿量是安德森杂质模型的变体，并通过基于大值的d-d库仑相互作用U_{d}和Lanczos矩阵对角化例程的物理动机基组减少来求解特征值来实现效率。模型参数的约束拟合的偏态密度（PDOS）从从头计算密度泛函理论计算。对于我们的模型的一个特定的应用，我们专注于电子转移发生在钴离子之间的铵溶剂化，将配置两种金属离子的多重态之间的相互作用。我们证明了该方法的能力，有效地计算绝热势能面和电子耦合因子，我们已经计算比较以及以前的计算和实验。
英文摘要：
We present a model intended for rapid sampling of ground and excited state potential energy surfaces for first-row transition metal active sites. The method is computationally inexpensive and is suited for dynamics simulations where (1) adiabatic states are required "on-the-fly" and (2) the primary source of the electronic coupling between the diabatic states is the perturbative spin-orbit interaction among the 3d electrons. The model Hamiltonian we develop is a variant of the Anderson impurity model and achieves efficiency through a physically motivated basis set reduction based on the large value of the d-d Coulomb interaction U_{d} and a Lanczos matrix diagonalization routine to solve for eigenvalues. The model parameters are constrained by fits to the partial density of states (PDOS) obtained from ab initio density functional theory calculations. For a particular application of our model we focus on electron-transfer occuring between cobalt ions solvated by ammonium, incorporating configuration interaction between multiplet states for both metal ions. We demonstrate the capability of the method to efficiently calculate adiabatic potential energy surfaces and the electronic coupling factor we have calculated compares well to previous calculations and experiment.
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