Self-consistent-field calculations of core excited states
Self-consistent-field calculations of core excited states
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DOI：
10.1063/1.3092928
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发表时间：
2009-03-28
影响因子：
4.4
通讯作者：
Gill, Peter M. W.
中科院分区：
文献类型：
--
作者：
Besley, Nicholas A.;Gilbert, Andrew T. B.;Gill, Peter M. W.
核心激发能和核心电子结合能计算的准确性内的德尔塔自洽场框架进行评估。通过使用称为最大重叠方法的重叠准则保持单个占据的核心轨道来防止核心激发态的变分崩溃。当应用到广泛的有机小分子，所产生的核心激发能不系统地低估所观察到的含时密度泛函理论和同意与实验。这种方法的核心激发态的准确性说明了前边缘功能的计算在X射线吸收光谱的质体蓝素，这表明，准确的结果可以实现与Delta自洽场计算时，与未收缩的基函数结合使用。
The accuracy of core excitation energies and core electron binding energies computed within a Delta self-consistent-field framework is assessed. The variational collapse of the core excited state is prevented by maintaining a singly occupied core orbital using an overlap criterion called the maximum overlap method. When applied to a wide range of small organic molecules, the resulting core excitation energies are not systematically underestimated as observed in time-dependent density functional theory and agree well with experiment. The accuracy of this approach for core excited states is illustrated by the calculation of the pre-edge features in x-ray absorption spectra of plastocyanin, which shows that accurate results can be achieved with Delta self-consistent-field calculations when used in conjunction with uncontracted basis functions.