Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, United Kingdom.
Department of Physics, University of Gothenburg, Origovägen 6B, SE-412 96 Gothenburg, Sweden.
J Chem Phys. 2019 Sep 21;151(11):114301. doi: 10.1063/1.5115552.
The triple ionization of HCl by double Auger decay and related processes has been studied using a multiparticle coincidence technique combined with synchrotron radiation. Four contributing processes are identified; direct double Auger, two indirect double Auger decay pathways, and single Auger decay from core-valence doubly ionized intermediate states. One indirect Auger process involves autoionization from superexcited states of Cl. Double Auger decay from HCl (2p, P), which makes up 11% ± 2% of total Auger decay, is estimated to be 40% direct, 15% indirect via atomic Cl and 45% indirect via molecular intermediate doubly ionized states. The vertical triple ionization energy of HCl is determined as 73.8 ± 0.5 eV. Molecular field effects are found to affect the direct double Auger process as well as normal single Auger decay. A comparison between spectra of the HCl and DCl isotopomers indicates that electronic decay is faster in all the processes than molecular dissociation.
使用多粒子符合技术结合同步辐射，研究了 HCl 的三重电离通过双俄歇衰变和相关过程。确定了四个贡献过程; 直接双俄歇、两种间接双俄歇衰变途径和来自核 - 价态双电离中间态的单俄歇衰变。间接俄歇过程之一涉及 Cl 的超激发态的自电离。构成总俄歇衰变的 11%±2%的 HCl (2p，P) 的双俄歇衰变，估计有 40%是直接的，15%是通过原子 Cl 间接的，45%是通过分子中间态双电离态间接的。HCl 的垂直三重电离能确定为 73.8±0.5 eV。发现分子场效应对直接双俄歇过程以及正常单俄歇衰变都有影响。HCl 和 DCl 同位素异构体的光谱比较表明，电子衰减在所有过程中都比分子离解快。
