Ab initio treatment of molecular Coster–Kronig decay using complex-scaled equation-of-motion coupled-cluster theory,Physical Chemistry Chemical Physics

当前位置： X-MOL 学术 › Phys. Chem. Chem. Phys. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Ab initio treatment of molecular Coster–Kronig decay using complex-scaled equation-of-motion coupled-cluster theory
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2024-08-27 , DOI: 10.1039/d4cp02085e
Jan Philipp Drennhaus ₁ , Anthuan Ferino-Pérez ₁ , Florian Matz ₁ , Thomas-C Jagau ₁

Affiliation

Vacancies in the L₁ shell of atoms and molecules can decay non-radiatively via Coster–Kronig decay whereby the vacancy is filled by an electron from the L_2,3 shell while a second electron is emitted into the ionization continuum. This process is akin to Auger decay, but in contrast to Auger electrons, Coster–Kronig electrons have rather low kinetic energies of less than 50 eV. In the present work, we extend recently introduced methods for the construction of molecular Auger spectra that are based on complex-scaled equation-of-motion coupled-cluster theory to Coster–Kronig decay. We compute ionization energies as well as total and partial decay widths for the 2s⁻¹ states of argon and hydrogen sulfide and construct the L₁L_2,3M Coster–Kronig and L₁MM Auger spectra of these species. Whereas our final spectra are in good agreement with the available experimental and theoretical data, substantial disagreements are found for various branching ratios suggesting that spin–orbit coupling makes a major impact on Coster–Kronig decay already in the third period of the periodic table.

中文翻译：

使用复杂尺度运动方程耦合簇理论从头计算分子 Coster-Kronig 衰变

原子和分子的 L ₁壳层中的空位可以通过Coster-Kronig 衰变进行非辐射衰变，其中空位由来自 L _2,3壳层的电子填充，同时第二个电子被发射到电离连续体中。这个过程类似于俄歇衰变，但与俄歇电子相比，科斯特-克罗尼格电子的动能相当低，低于 50 eV。在目前的工作中，我们将最近引入的基于复杂尺度运动方程耦合簇理论的分子俄歇谱构建方法扩展到科斯特-克罗尼格衰变。我们计算了氩和硫化氢的 2s ^-1态的电离能以及总和部分衰变宽度，并构建了这些物质的 L ₁ L _2,3 M Coster-Kronig 和 L ₁ MM 俄歇光谱。虽然我们的最终光谱与现有的实验和理论数据非常一致，但在各种支化比方面发现了很大的分歧，这表明自旋轨道耦合已经对元素周期表第三周期的科斯特-克罗尼格衰变产生了重大影响。

更新日期：2024-08-27

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南