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Anomalous Property of Ag(BO 2 ) 2 Hyperhalogen: Does Spin–Orbit Coupling Matter?
Author(s) -
Chen Hui,
Kong XiangYu,
Zheng Weijun,
Yao Jiannian,
Kandalam Anil K.,
Jena Puru
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201300677
Subject(s) - x ray photoelectron spectroscopy , ab initio quantum chemistry methods , electronic structure , ionic bonding , ab initio , chemistry , spin–orbit interaction , density functional theory , metal , coupling (piping) , crystallography , relativistic quantum chemistry , atomic physics , computational chemistry , ion , materials science , condensed matter physics , molecule , physics , nuclear magnetic resonance , organic chemistry , metallurgy
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(BO 2 ) 2 − , Ag(BO 2 ) 2 − , and Au(BO 2 ) 2 − . The vertical electron detachment energy (VDE) of Ag(BO 2 ) 2 − is anomalously higher than those of Au(BO 2 ) 2 − and Cu(BO 2 ) 2 − . In quantitative agreement with the experiment, high‐level ab initio calculations reveal that spin–orbit coupling (SOC) lowers the VDE of Au(BO 2 ) 2 − significantly. The sizable magnitude of about 0.5 eV of SOC effect on the VDE of Au(BO 2 ) 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 Au I L 2 complexes, which is characterized by a substantial SOC effect.