Density functional computations for inner-shell excitation spectroscopy
Density functional computations for inner-shell excitation spectroscopy
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DOI：
10.1016/s0009-2614(96)01125-6
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发表时间：
1996-11-29
影响因子：
2.8
通讯作者：
Chong, DP
中科院分区：
文献类型：
--
作者：
Hu, CH;Chong, DP
利用密度泛函理论和无限制广义过渡态（uGTS）方法研究了7个分子的1s—> π *内壳激发谱。交换相关势是基于Becke的交换（B88）和Perdew的相关（P86）的组合函数。基于Clementi和Raimondi的原子筛选规则的标度程序应用于cc-pVTZ基原子集，其中在uGTS计算中创建了部分核心孔。我们预测的1s -> π *激发能与实验值之间的平均绝对偏差仅为0.16 eV。CO、C2H2、C2H4和C6H6的c1s—> π *跃迁的单重三倍分裂也符合实验观察。我们预测的核心电子结合能和项值的平均绝对偏差分别为0.23和0.29 eV。
The 1s --> pi* inner-shell excitation spectra of seven molecules have been studied using density functional theory along with the unrestricted generalized transition state (uGTS) approach. The exchange-correlation potential is based on a combined functional of Becke's exchange (B88) and Perdew's correlation (P86). A scaling procedure based on Clementi and Raimondi's rules for atomic screening is applied to the cc-pVTZ basis set of atoms where a partial core-hole is created in the uGTS calculations. The average absolute deviation between our predicted 1s --> pi* excitation energies and experimental values is only 0.16 eV. Singlet-tripler splittings of C 1s --> pi* transitions of CO, C2H2, C2H4, and C6H6 also agree with experimental observations. The average absolute deviation of our predicted core-electron binding energies and term values is 0.23 and 0.29 eV, respectively.