Forbes Ruaridh, Hockett Paul, Powis Ivan, Bozek John D, Pratt Stephen T, Holland David M P
PULSE Institute, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025, USA.
National Research Council of Canada, 100 Sussex Dr. Ottawa, ON K1A 0R6, Canada.
Phys Chem Chem Phys. 2022 Jan 19;24(3):1367-1379. doi: 10.1039/d1cp04797c.
Linearly polarized synchrotron radiation has been used to record polarization dependent, non-resonant Auger electron spectra of XeF, encompassing the bands due to the xenon MNN, MNN, MNN and MNV and fluorine KVV transitions. Resonantly excited Auger spectra have been measured at photon energies coinciding with the Xe 3d → σ* and the overlapped Xe 3d/F 1s → σ* excitations in XeF. The non-resonant and resonantly excited spectra have enabled the Auger electron angular distributions, as characterized by the parameter, to be determined for the MNN transitions. In the photon energy range over which the Auger electron angular distributions were measured, theoretical results indicate that transitions into the f continuum channel dominate the Xe 3d photoionization in XeF. In this limit, the theoretical value of the atomic alignment parameter () characterizing the core ionized state becomes constant. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters () from the parameters extracted from our non-resonant Auger spectra. For a particular Auger transition, the electron kinetic energy measured in the resonantly excited spectrum is higher than that in the directly ionized spectrum, due to the screening provided by the electron promoted into the σ* orbital. The interpretation of the F KVV Auger band in XeF has been discussed in relation to previously published one-site populations of the doubly charged ions (XeF). The experimental results show that the ionization energies of the doubly charged states predominantly populated in the decay of a vacancy in the F 1s orbital in XeF tend to be higher than those populated in the decay of a vacancy in the Xe 4d level in XeF.
线偏振同步辐射已被用于记录XeF的偏振相关非共振俄歇电子能谱,涵盖了氙的MNN、MNN、MNN和MNV以及氟的KVV跃迁所产生的谱带。在与XeF中Xe 3d→σ以及重叠的Xe 3d/F 1s→σ激发相一致的光子能量下测量了共振激发俄歇能谱。非共振和共振激发能谱使得能够确定MNN跃迁的以参数表征的俄歇电子角分布。在测量俄歇电子角分布的光子能量范围内,理论结果表明,向f连续谱通道的跃迁在XeF的Xe 3d光电离中占主导。在此极限下,表征核心电离态的原子排列参数()的理论值变得恒定。该理论值已被用于从我们的非共振俄歇能谱中提取的参数获得俄歇电子本征各向异性参数()。对于特定的俄歇跃迁,由于被激发到σ*轨道的电子提供的屏蔽作用,在共振激发能谱中测量的电子动能高于直接电离能谱中的电子动能。已结合先前发表的双电荷离子(XeF)的单中心布居情况讨论了XeF中F KVV俄歇谱带的解释。实验结果表明,在XeF中F 1s轨道空位衰变中主要布居的双电荷态的电离能往往高于XeF中Xe 4d能级空位衰变中布居的双电荷态的电离能。