Theory and ab initio calculations of 2p photoabsorption spectra: The lowest Rydberg resonances in HCl
Theory and ab initio calculations of 2p photoabsorption spectra: The lowest Rydberg resonances in HCl
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2p 光吸收光谱的理论和从头计算：HCl 中的最低里德伯共振
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
H. Aksela
中科院分区：
文献类型：
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作者：
R. Fink;Mika Kivilompolo;H. Aksela
我们提出了线性分子 2p 核心激发光谱的理论，其中明确包括 2p 核心轨道的自旋轨道分裂以及所有非相对论效应。这适用于 HCl 在 2p→6σ*、4s、4p、3d 和 5s 共振能量处的吸收光谱。谱图的所有输入数据均通过从头计算获得。这些是（i）贡献态的非相对论能量和跃迁概率，（ii）自旋轨道耦合参数，以及（iii）核心激发态的总俄歇跃迁率。理论和实验吸收光谱的比较支持了先前的理论发现，即总俄歇衰减率基本上取决于芯孔方向。此外，还讨论了核心激发 HCl 分子相对于分子键轴的择优取向。基础上给出了 2p3/2 和 2p1/2 孔对应态之间强度比的一般考虑。
We present a theory for 2p core excitation spectra of linear molecules that explicitly includes the spin-orbit splitting of the 2p core orbitals as well as all nonrelativistic effects. This is applied to the absorption spectrum of HCl at the 2p→6σ*, 4s, 4p, 3d, and 5s resonance energies. All input data for the spectrum are obtained from ab initio calculations. These are (i) the nonrelativistic energies and transition probabilities of the contributing states, (ii) the spin-orbit coupling parameter, and (iii) the total Auger transition rates of the core excited states. The prior theoretical finding that the total Auger decay rate depends substantially on the core hole orientation is supported by a comparison of the theoretical and experimental absorption spectra. Furthermore, the preferred orientation of the core excited HCl molecule with respect to the molecular bond axis is discussed. General considerations about intensity ratios between corresponding states with 2p3/2 and 2p1/2 holes are given on the bas...