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

被引：13

作者：

Chen, Hui ^{[1
]}

Kong, Xiang-Yu ^{[2
]}

Zheng, Weijun ^{[2
]}

Yao, Jiannian ^{[1
]}

Kandalam, Anil K. ^{[3
]}

Jena, Puru ^{[4
]}

机构：

[1] Chinese Acad Sci, Inst Chem, CAS Key Lab Photochem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China

[2] Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China

[3] W Chester Univ, Dept Phys, W Chester, PA 19383 USA

[4] Virginia Commonwealth Univ, Dept Phys, Richmond, VA 23284 USA

来源：

CHEMPHYSCHEM | 2013年 / 14卷 / 14期

基金：

美国国家科学基金会;

关键词：

ab initio calculation; coinage metals; hyperhalogen; photoelectron spectroscopy; spin-orbit coupling; RESOLVED PHOTOELECTRON-SPECTROSCOPY; ELECTRONIC-STRUCTURE; BINDING-ENERGIES; NEGATIVE-IONS; BASIS-SETS; GROUP-11; AG; CU; AFFINITIES; POTENTIALS;

D O I：

10.1002/cphc.201300677

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 (AuL2)-L-I complexes, which is characterized by a substantial SOC effect.

引用

页码：3303 / 3308

页数：6

共 51 条

[31] Superhalogen oxidizers capable of ionizing water molecules [J].

Marchaj, Marzena ;

Freza, Sylwia ;

Rybacka, Olimpia ;

Skurski, Piotr .

CHEMICAL PHYSICS LETTERS, 2013, 574 :13-17

[32] Ab initio total atomization energies of small molecules - Towards the basis set limit [J].

Martin, JML .

CHEMICAL PHYSICS LETTERS, 1996, 259 (5-6) :669-678

[33] Importance of spin-orbit coupling for the assignment of the photodetachment spectra of AuX2 (X = Cl, Br, and I) [J].

Mishra, S ;

Vallet, V ;

Domcke, W .

CHEMPHYSCHEM, 2006, 7 (03) :723-727

[34] Borane Derivatives: A New Class of Super- and Hyperhalogens [J].

Pathak, Biswarup ;

Samanta, Devleena ;

Ahuja, Rajeev ;

Jena, Purusottam .

CHEMPHYSCHEM, 2011, 12 (13) :2423-2428

[35]

Perdew JP, 1997, PHYS REV LETT, V78, P1396, DOI 10.1103/PhysRevLett.77.3865

[36] Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements [J].

Peterson, KA ;

Puzzarini, C .

THEORETICAL CHEMISTRY ACCOUNTS, 2005, 114 (4-5) :283-296

[37] NATURAL-POPULATION ANALYSIS [J].

REED, AE ;

WEINSTOCK, RB ;

WEINHOLD, F .

JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (02) :735-746

[38] Moderately Reactive Molecules Forming Stable Ionic Compounds with Superhalogens [J].

Sikorska, Celina ;

Skurski, Piotr .

INORGANIC CHEMISTRY, 2011, 50 (13) :6384-6391

[39] Effect of spin-orbit coupling on reduction potentials of octahedral ruthenium(II/III) and osmium(II/III) complexes [J].

Srnec, Martin ;

Chalupsky, Jakub ;

Fojta, Miroslav ;

Zendlova, Lucie ;

Havran, Ludek ;

Hocek, Michal ;

Kyvala, Mojmir ;

Rulisek, Lubomir .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (33) :10947-10954

[40] First experimental photoelectron spectra of superhalogens and their theoretical interpretations [J].

Wang, XB ;

Ding, CF ;

Wang, LS ;

Boldyrev, AI ;

Simons, J .

JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (10) :4763-4771

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