AuO: Evolving from Dis- to Comproportionation and Back Again

Andreas Hermann; Mariana Derzsi; Wojciech Grochala; Roald Hoffmann

doi:10.1021/acs.inorgchem.5b02528

AuO: Evolving from Dis- to Comproportionation and Back Again

Andreas Hermann, Mariana Derzsi, Wojciech Grochala, Roald Hoffmann

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Abstract

The structural, electronic, and dynamic properties of hypothetical gold(II) oxide (AuO) are studied theoretically, at atmospheric and elevated pressures, with the use of hybrid density functional theory. At p = 1 atm, hypothetical AuO (metastable with respect to the elements) is predicted to crystallize in a new structure type, unique among the late-transition-metal monoxides, with disproportionation of the Au ions to AuI/III and featuring aurophilic interactions. Under pressure, familiar structure types are stabilized: a semiconducting AgO-type structure at ∼2.5 GPa and, with a further increase of the pressure up to ∼80 GPa, an AuSO4-type structure containing Au2 pairs. Finally, above 105 GPa, distorted NaCl- and CsCl-type AuIIO structures dominate, and metallization is predicted at 329 GPa.

Original language	English (US)
Pages (from-to)	1278-1286
Number of pages	9
Journal	Inorganic Chemistry
Volume	55
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02528
State	Published - Jan 21 2016
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): k128
Acknowledgements: A.H. and R.H. are grateful for support from EFree, an Energy Frontier Research Center, funded by the U.S. Department of Energy (Grant DESC0001057 at Cornell University), and from the U.S. National Science Foundation (Grant CHE-0910623). W.G. and M.D. acknowledge financial support from the Polish National Science Centre (NCN; Project HP 2012/06/M/ST5/00344). Computational resources provided by the Cornell NanoScale Facility (supported by the National Science Foundation through Grant ECS-0335765), the XSEDE network (provided by the National Center for Supercomputer Applications through Grant TG-DMR060055N), the KAUST Supercomputing Laboratory (Project ID k128), and the UK National Supercomputing Service (ARCHER Project ID d56) are gratefully acknowledged. Calculations at University of Warsaw were performed on ICM machines within Project G29-3.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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title = "AuO: Evolving from Dis- to Comproportionation and Back Again",

abstract = "The structural, electronic, and dynamic properties of hypothetical gold(II) oxide (AuO) are studied theoretically, at atmospheric and elevated pressures, with the use of hybrid density functional theory. At p = 1 atm, hypothetical AuO (metastable with respect to the elements) is predicted to crystallize in a new structure type, unique among the late-transition-metal monoxides, with disproportionation of the Au ions to AuI/III and featuring aurophilic interactions. Under pressure, familiar structure types are stabilized: a semiconducting AgO-type structure at ∼2.5 GPa and, with a further increase of the pressure up to ∼80 GPa, an AuSO4-type structure containing Au2 pairs. Finally, above 105 GPa, distorted NaCl- and CsCl-type AuIIO structures dominate, and metallization is predicted at 329 GPa.",

author = "Andreas Hermann and Mariana Derzsi and Wojciech Grochala and Roald Hoffmann",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): k128 Acknowledgements: A.H. and R.H. are grateful for support from EFree, an Energy Frontier Research Center, funded by the U.S. Department of Energy (Grant DESC0001057 at Cornell University), and from the U.S. National Science Foundation (Grant CHE-0910623). W.G. and M.D. acknowledge financial support from the Polish National Science Centre (NCN; Project HP 2012/06/M/ST5/00344). Computational resources provided by the Cornell NanoScale Facility (supported by the National Science Foundation through Grant ECS-0335765), the XSEDE network (provided by the National Center for Supercomputer Applications through Grant TG-DMR060055N), the KAUST Supercomputing Laboratory (Project ID k128), and the UK National Supercomputing Service (ARCHER Project ID d56) are gratefully acknowledged. Calculations at University of Warsaw were performed on ICM machines within Project G29-3. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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doi = "10.1021/acs.inorgchem.5b02528",

language = "English (US)",

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journal = "Inorganic Chemistry",

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AU - Hermann, Andreas

AU - Derzsi, Mariana

AU - Grochala, Wojciech

AU - Hoffmann, Roald

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): k128 Acknowledgements: A.H. and R.H. are grateful for support from EFree, an Energy Frontier Research Center, funded by the U.S. Department of Energy (Grant DESC0001057 at Cornell University), and from the U.S. National Science Foundation (Grant CHE-0910623). W.G. and M.D. acknowledge financial support from the Polish National Science Centre (NCN; Project HP 2012/06/M/ST5/00344). Computational resources provided by the Cornell NanoScale Facility (supported by the National Science Foundation through Grant ECS-0335765), the XSEDE network (provided by the National Center for Supercomputer Applications through Grant TG-DMR060055N), the KAUST Supercomputing Laboratory (Project ID k128), and the UK National Supercomputing Service (ARCHER Project ID d56) are gratefully acknowledged. Calculations at University of Warsaw were performed on ICM machines within Project G29-3. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2016/1/21

Y1 - 2016/1/21

N2 - The structural, electronic, and dynamic properties of hypothetical gold(II) oxide (AuO) are studied theoretically, at atmospheric and elevated pressures, with the use of hybrid density functional theory. At p = 1 atm, hypothetical AuO (metastable with respect to the elements) is predicted to crystallize in a new structure type, unique among the late-transition-metal monoxides, with disproportionation of the Au ions to AuI/III and featuring aurophilic interactions. Under pressure, familiar structure types are stabilized: a semiconducting AgO-type structure at ∼2.5 GPa and, with a further increase of the pressure up to ∼80 GPa, an AuSO4-type structure containing Au2 pairs. Finally, above 105 GPa, distorted NaCl- and CsCl-type AuIIO structures dominate, and metallization is predicted at 329 GPa.

AB - The structural, electronic, and dynamic properties of hypothetical gold(II) oxide (AuO) are studied theoretically, at atmospheric and elevated pressures, with the use of hybrid density functional theory. At p = 1 atm, hypothetical AuO (metastable with respect to the elements) is predicted to crystallize in a new structure type, unique among the late-transition-metal monoxides, with disproportionation of the Au ions to AuI/III and featuring aurophilic interactions. Under pressure, familiar structure types are stabilized: a semiconducting AgO-type structure at ∼2.5 GPa and, with a further increase of the pressure up to ∼80 GPa, an AuSO4-type structure containing Au2 pairs. Finally, above 105 GPa, distorted NaCl- and CsCl-type AuIIO structures dominate, and metallization is predicted at 329 GPa.

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SP - 1278

EP - 1286

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

AuO: Evolving from Dis- to Comproportionation and Back Again

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