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Electronic structures and optical properties of cuprous oxide and hydroxide
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Technology.
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Technology.ORCID iD: 0000-0002-0086-5536
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Technology.ORCID iD: 0000-0002-9920-5393
2014 (English)In: Materials Research Society Symposium Proceedings, ISSN 0272-9172, Vol. 1675, 185-190 p.Article in journal (Refereed) Published
Abstract [en]

The broad range of applications of copper, including areas such as electronics, fuel cells, and spent nuclear fuel disposal, require accurate description of the physical and chemical properties of copper compounds. Within some of these applications, cuprous hydroxide is a compound whose relevance has been recently discovered. Its existence in the solid-state form was recently reported. Experimental determination of its physical-chemical properties is challenging due to its instability and poop crystallinity. Within the framework of density functional theory calculations (DFT), we investigated the nature of bonding, electronic spectra, and optical properties of the cuprous oxide and cuprous hydroxide. It is found that the hybrid functional PBEO can accurately describe the electronic structure and optical properties of these two copper(I) compounds. The calculated properties of cuprous oxide are in good agreement with the experimental data and other theoretical results. The structure of cuprous hydroxide can be deduced from that of cuprous oxide by substituting half Cu∗ in Cu2O lattice with protons. Compared to CU2O, the presence of hydrogen in CuOH has little effect on the ionic nature of Cu-O bonding, but lowers the energy levels of the occupied states. Thus, CuOH is calculated to have a wider indirect band gap of 2.73 eV compared with the Cu2O band gap of 2.17 eV.

Place, publisher, year, edition, pages
2014. Vol. 1675, 185-190 p.
Keyword [en]
Chemical bonds, Chemical compounds, dioactive wastes
National Category
Materials Engineering
URN: urn:nbn:se:kth:diva-168526DOI: 10.1557/opl.2014.862ScopusID: 2-s2.0-84922434279OAI: diva2:818733
2014 MRS Spring Meeting; San Francisco; United States

QC 20150609

Available from: 2015-06-09 Created: 2015-06-04 Last updated: 2015-08-13Bibliographically approved
In thesis
1. Ab initio based modeling of defects and disorder in industrial materials
Open this publication in new window or tab >>Ab initio based modeling of defects and disorder in industrial materials
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The study of defects and disorder in condensed matter remains a central subject of materials science. Newly emerging experimental and theoretical techniques promote our understanding in this field, and reveal many interesting phenomena in which the atomic picture plays a crucial role. In this thesis we present a study on the fundamental and applied aspects of defects and disorder in industrial materials.

We consider the basic aspects of defective and disordered crystals, and discuss the structural, electronic, thermodynamic and mechanical properties of such materials. In particular, we have systematically investigated the defects in copper metal based on ab initio calculations. The point defects, point defects interactions, stacking faults, and the grain boundaries have been studied. Efforts are made to relate the atomistic information to the macroscopic mechanical behavior of copper metal possessing defects. The stackingfault energy of copper is found to be sensitive to the change of temperature and the presence of point defects. The atomic size effect of phosphorous is more evident for the change of the stacking-fault energy of copper among the 3sp impurities. While the change of the work of separation of grain boundary is found to follow the pattern of the chemical effect. When the chemical effect dominates, the impurity enhances the cohesion strength of grain boundary, and vice versa. The study well explains the various influence of the defects on the macroscopic mechanical properties of copper, including the anomalous behaviour of phosphorous in copper.

The structure and properties of monovalent copper compounds with oxygen and/or hydrogen were also explored. The ground-state cuprice–CuOH(s) was identified using a combined theoretical-experimental effort. The structure determined with DFT was validated by comparison with the X-ray diffraction data obtained from the synthesized material. The ground-state structure of CuOH(s) has a layered structure that is stabilized by antiferroelectric cation ordering which, in turn, is caused by collective electrostatic interactions. The electronic and thermodynamic properties of the cationordered CuOH(s) are intimately linked to the bonding topology in this material, which is composed of one-dimensional (folded and interlocked chains) and two-dimensional (layers) structural units. The solid CuOH is an indirect band gap semiconductor, while the band gap varies between 2.73 eV and 3.03 eV due to cation disorder. The hydrogen in CuOH has little effect on the ionic nature of the Cu–O bonding relative to that in Cu2O, but lowers the energy levels of the occupied states by giving a covalent character to the O–H bond. The competing structures of copper hydride were also investigated. Structure–property relationships were analyzed on this series of materials to gain fundamental understanding of their behaviour.

Defects and disorder are also important for understanding the structure γ-alumina. Our calculations have confirmed that the most stable structure of γ-alumina is the defective spinel phase with disordered cation vacancies. The hydrogenated spinel phase is also dynamically stable, but thermodynamically unstable with respect to the defective spinel phase and H2O, as well as relative to the defective spinel phase and Boehmite (γ- AlO(OH)). This is in spite of the high entropy content of hydrogenated γ-alumina. Our calculations and analysis allow us to conclude that the hydrogenated spinel structure is only a metastable phase that forms during the decomposition of Boehmite above 753 K. However, dehydration of the metastable phase into the ground state is expected to be a slow process due to the low diffusion rate of H, which leaves hydrogen as a locked-in impurity in γ-alumina under conditions of normal temperature and pressure.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. viii, 93 p.
National Category
Condensed Matter Physics
Research subject
Materials Science and Engineering
urn:nbn:se:kth:diva-170617 (URN)978-91-7595-640-4 (ISBN)
Public defence
2015-08-28, Sal E2,, Lindstedtvägen 3, KTH, Stockholm, 10:00 (English)
Swedish Radiation Safety Authority

QC 20150813

Available from: 2015-08-13 Created: 2015-07-01 Last updated: 2015-08-13Bibliographically approved

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