Gold with +4 and +6 Oxidation States in AuF<sub>4</sub> and AuF<sub>6</sub>

Lin, Jianyan; Zhang, Shoutao; Guan, Wei; Yang, Guochun; Ma, Yanming

doi:10.1021/jacs.8b04563

Cited by 84 publications

(105 citation statements)

References 108 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…It is well accepted that pressure favors the stabilization of unusual stoichiometric compounds [41][42][43][44], exhibiting interesting physical and chemical properties. For example, several stable sulfur hydrides (e.g., H 2 S 3 , H 3 S 2 , HS 2 , H 3 S, and H 4 S 3 ) [45][46][47] have been identified at high pressures.…”

Section: Introductionmentioning

confidence: 99%

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Zhang

Lin

et al. 2019

Phys. Rev. B

Self Cite

View full text Add to dashboard Cite

Pressure has become an effective way to obtain new materials with desirable properties. Considering the various stoichiometries, wide applications, and unique structures of binary H-S, H-B, and B-S compounds, especially at high pressures, it is worth expecting that they might form ternary compounds with interesting properties as well. Here, phase stabilities of H-B-S ternary compounds, in the pressure range from 0 to 200 GPa, are reliably determined through first-principles unbiased structural search calculations. A hitherto unknown orthorhombic HBS compound with Ama2 symmetry is identified to be stable above 25 GPa, in which B and S atoms alternate to form distorted chains and H atoms are covalently bonded with Bs. With pressure, Ama2 HBS undergoes a semiconductor-to-metal electronic transition and even becomes superconducting. The exploration of the binary B-S phase diagram indicates that B-S compounds tend to decompose into elemental solids above 208 GPa. However, two S-rich phases, B 2 S 3 and BS 2 , are predicted at low pressures, exhibiting semiconducting and metallic properties, respectively. BS 2 shows a calculated T c value of 21.9 K at 200 GPa, becoming a superconductor among bulk binary B-S compounds.

show abstract

Section: Introductionmentioning

confidence: 99%

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Zhang

Lin

et al. 2019

Phys. Rev. B

Self Cite

View full text Add to dashboard Cite

show abstract

“…It becomes widely accepted that pressure can effectively overcome reaction energy barriers, shorten interatomic distances, and reorder atomic orbital energy levels . Thus, pressure has become a useful tool to discover unusual stoichiometric compounds with excellent chemical and physical properties ,,. In view of strong oxidation ability of O and S, once O‐ or S‐rich Au−O or S compounds are stabilized under high pressure, one might anticipate the presence of novel or mixed oxidation states of Au.…”

Section: Introductionmentioning

confidence: 99%

Mixed‐valence Compounds: AuO₂ and AuS

Tang

Zhang

et al. 2018

ChemPhysChem

Self Cite

View full text Add to dashboard Cite

Mixed-valence compounds are of great interest due to their interesting properties and wide applications. Recently, gold (Au) chemistry has experienced an unprecedented development. However, Au with mixed-valence states in Au-O compounds has not been reported thus far. Here, two hitherto unknown AuO and AuS compounds with mixed-valence character were identified with the aid of first-principles swarm structure searching calculations. AuO consists of quasi-square AuO moiety and AuO octahedron in which Au shows the mixed-valence states of III and V, the first example in Au-O binary compounds. AuS contains the linear AuS and quasi-square AuS units exhibiting Au mixed-valence states. The analysis of electronic property demonstrates that AuO and AuS are narrow band gap semiconductors with strong hybridization between Au 5d and O 2p or S 3p. With the increase of pressure, Au-O and Au-S compounds show completely different thermodynamic stabilities, resulting from distinct shifting of pressure-induced atomic orbital energy levels of O and S atoms. Our work provides an opportunity for understanding mixed-valence character in Au-O and Au-S compounds.

show abstract

“…However, band structure contributions are vital for an accurate description of the optical properties of gold nano‐structures and the AuH bond exhibits strong covalent character . Interestingly, small charge transfer has been found in the case of hydrides while recent work on gold fluorides shows more significant charge transfer . In the present case, the screening of a proton by the electron gas is important.…”

Section: Resultsmentioning

confidence: 77%

Synthesis and Properties of Au Hydride

et al. 2019

View full text Add to dashboard Cite

The generation of chemical species from gases, noble metals and light interacting with localized surface plasmons represents a new paradigm for achieving low energy sustainable reaction pathways. Here, we demonstrate that the dissociation reaction of H 2 meditated by the decay of localized surface plasmons of gold nanoparticles leads to the generation of a new material as detected by a change in the optical properties of the gold nanostructures. The effective permittivity measured by in situ spectroscopic ellipsometry shows a blue-shift of 0.02 eV in the surface plasmon resonance, demonstrating the plausible formation of a metastable gold hydride layer on the surface of nanoparticles following the dissociation of H 2 . The formation of this gold hydride through the interaction of gold with atomic H is supported by first-principles simulations. These calculations do not indicate a significant charge transfer upon hydrogenation of the (111) surface but rather large Friedel charge oscillations within the gold layer. Moreover, our blue-shift is produced by the formation of a hydride leading to changes in critical band gaps in the electronic structure. For a coverage of 11%, the calculated peak of the imaginary part of the ZZcomponent of the dielectric tensor undergoes a blue shift of 28 nm from a hydrogen free peak at 574 nm.[a] Dr.

show abstract

Gold with +4 and +6 Oxidation States in AuF₄ and AuF₆

Cited by 84 publications

References 108 publications

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Mixed‐valence Compounds: AuO₂ and AuS

Synthesis and Properties of Au Hydride

Contact Info

Product

Resources

About

Gold with +4 and +6 Oxidation States in AuF4 and AuF6

Cited by 84 publications

References 108 publications

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Phase diagrams and electronic properties of B-S and H-B-S systems under high pressure

Mixed‐valence Compounds: AuO2 and AuS

Synthesis and Properties of Au Hydride

Contact Info

Product

Resources

About

Gold with +4 and +6 Oxidation States in AuF₄ and AuF₆

Mixed‐valence Compounds: AuO₂ and AuS