Electron binding energies of anionic alkali metal atoms from partial fourth order electron propagator theory calculations
Electron binding energies of anionic alkali metal atoms from partial fourth order electron propagator theory calculations
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DOI：
10.1063/1.455401
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发表时间：
1988-11
影响因子：
4.4
通讯作者：
J. V. Ortiz
中科院分区：
文献类型：
--
作者：
J. V. Ortiz
Li−、Na−、K−、Rb− 和 Cs− 的电离能是用从头算电子传播理论计算的。 K、Rb 和 Cs 采用有效核心电势。对库普曼斯定理的三阶对角自能修正增加了四阶项，这些项很容易从三阶计算的副产品中确定。该部分四阶过程是使用超算子理论导出的。对于这些系统，证明了该方法相对于外价对角线近似的优越性。研究了关于传播子自能中电子相互作用的顺序和基组改进的结果的重叠。实验结果的一致性在 0.1 eV 以内。分析了其余的误差源。
Ionization energies of Li−, Na−, K−, Rb−, and Cs− are calculated with ab initio electron propagator theory. Effective core potentials are employed for K, Rb, and Cs. Third order diagonal self‐energy corrections to Koopmans’s theorem are augmented with fourth order terms that are easily determined from by‐products of a third order calculation. This partial fourth order procedure is derived using superoperator theory. The superiority of this method to an outer valence diagonal approximation is demonstrated for these systems. Covergence of results with respect to the order of electron interaction in the propagator self‐energy and with respect to basis set improvement is studied. Agreement to within 0.1 eV of experiment is achieved. Remaining sources of error are analyzed.