MC-SCF. I. The multi-configuration self-consistent-field method
MC-SCF. I. The multi-configuration self-consistent-field method
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DOI：
10.1063/1.1680022
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发表时间：
1973-12
影响因子：
4.4
通讯作者：
J. Hinze
中科院分区：
文献类型：
--
作者：
J. Hinze
提出了一种通用的多组态自洽场（MC-SCF）方法，该方法对参与展开总波函数的组态类型没有限制。导出了用于这种多组态波函数的“最佳”轨道的一般耦合Fock方程。形式上，这些耦合的非线性方程组解耦与投影算子的使用，并转化为一个伪特征值问题。基于轨道变换和广义布里渊定理，给出了几种求解耦合非线性类Fock方程的一般方法，用于确定MC-SCF轨道。所提出的形式主义不仅适用于给定系统的基态，而且适用于任何激发态，从而得到所需状态的真能量的上限。
The general multi‐configuration self‐consistent‐field (MC‐SCF) method is presented with no restrictions on the types of configurations participating in the expansion of the total wavefunction. The general coupled Fock‐like equations for the ``best'' orbitals to be used in such a multi‐configuration wavefunction are derived. Formally these coupled nonlinear equations are decoupled with the use of projection operators and transformed into a pseudoeigenvalue problem. Several general methods, based on orbital transformations and on the use of the generalized Brillouin theorem, are presented for solving the coupled nonlinear Fock like equations for the determination of the MC‐SCF orbitals. The formalism presented is applicable not only to the ground state of a given system, but also to any excited state, yielding an upper bound to the true energy of the desired state.