Extension of the Core-Valence-Rydberg B3LYP Functional to Core-Excited-State Calculations of Third-Row Atoms.
Extension of the Core-Valence-Rydberg B3LYP Functional to Core-Excited-State Calculations of Third-Row Atoms.
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DOI：
10.1021/ct600368f
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发表时间：
2007-07
影响因子：
5.5
通讯作者：
A. Nakata;Y. Imamura;H. Nakai
中科院分区：
文献类型：
--
作者：
A. Nakata;Y. Imamura;H. Nakai
提出了一种修正的核价Rydberg Becke三参数交换（B3）+ Lee-Yang-Parr（LYP）关联（CVR-B3 LYP）泛函，用于计算第三排原子的核激发能.传统的交换相关泛函的评估表明，适当的部分Hartree-Fock（HF）交换芯激发态计算取决于壳：70%和50%的K-壳和L-壳激发，分别。因此，经修饰的CVR-B3 LYP泛函被设计为分别使用适当部分的HF交换，70%、50%和20%用于K-壳层、L-壳层和价区。用改进的CVR-B3 LYP泛函进行含时密度泛函理论计算，得到K-壳层和L-壳层的激发能，具有合理的精度。修正的CVR-B3 LYP也提供了价激发能和标准的形成准确。因此，修改的CVR-B3 LYP适当地描述了所有的K-壳层、L-壳层和价电子。
A modified core-valence-Rydberg Becke's three-parameter exchange (B3) + Lee-Yang-Parr (LYP) correlation (CVR-B3LYP) functional is proposed in order to calculate core-excitation energies of third-row atoms with reasonable accuracy. The assessment of conventional exchange-correlation functionals shows that the appropriate portions of Hartree-Fock (HF) exchange for core-excited-state calculations depend on shells: 70% and 50% for K-shell and L-shell excitations, respectively. Therefore, the modified CVR-B3LYP functional is designed to use the appropriate portions of HF exchange, 70%, 50%, and 20%, for K-shell, L-shell, and valence regions separately. Time-dependent density functional theory calculations with the modified CVR-B3LYP functional yield both K-shell and L-shell excitation energies with reasonable accuracy. The modified CVR-B3LYP also provides valence-excitation energies and standard enthalpies of formation accurately. Thus, the modified CVR-B3LYP describes all of the K-shell, L-shell, and valence electrons appropriately.