Anomalous Property of Ag(BO2)2 Hyperhalogen: Does Spin–Orbit Coupling Matter?

Authors

  • Prof. Dr. Hui Chen,

    Corresponding author
    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (China)
    • Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (China)
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  • Xiang-Yu Kong,

    1. State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, CAS, Beijing 100190 (China)
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  • Prof. Dr. Weijun Zheng,

    Corresponding author
    1. State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, CAS, Beijing 100190 (China)
    • State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, CAS, Beijing 100190 (China)
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  • Prof. Dr. Jiannian Yao,

    1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (China)
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  • Prof. Dr. Anil K. Kandalam,

    1. Department of Physics, West Chester University, West Chester, PA 19383 (USA)
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  • Prof. Dr. Puru Jena

    1. 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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