Anomalous Property of Ag(BO2)2 Hyperhalogen: Does Spin–Orbit Coupling Matter? |
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| Authors: | Prof Dr Hui Chen Xiang‐Yu Kong Prof Dr Weijun Zheng Prof Dr Jiannian Yao Prof Dr Anil K Kandalam Prof Dr Puru Jena |
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| Institution: | 1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (China);2. State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, CAS, Beijing 100190 (China);3. Department of Physics, West Chester University, West Chester, PA 19383 (USA);4. Department of Physics, Virginia Commonwealth University, Richmond, VA 23284 (USA) |
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| Abstract: | Hyperhalogens were recently identified as a new class of highly electronagative species which are composed of metals and superhalogens. In this work, high‐level theoretical calculations and photoelectron spectroscopy experiments are systematically conducted to investigate a series of coinage‐metal‐containing hyperhalogen anions, Cu(BO2)2?, Ag(BO2)2?, and Au(BO2)2?. The vertical electron detachment energy (VDE) of Ag(BO2)2? is anomalously higher than those of Au(BO2)2? and Cu(BO2)2?. In quantitative agreement with the experiment, high‐level ab initio calculations reveal that spin–orbit coupling (SOC) lowers the VDE of Au(BO2)2? significantly. The sizable magnitude of about 0.5 eV of SOC effect on the VDE of Au(BO2)2? demonstrates that SOC plays an important role in the electronic structure of gold hyperhalogens. This study represents a new paradigm for relativistic electronic structure calculations for the one‐electron‐removal process of ionic AuIL2 complexes, which is characterized by a substantial SOC effect. |
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| Keywords: | ab initio calculation coinage metals hyperhalogen photoelectron spectroscopy spin– orbit coupling |
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