Electronic structure and bonding properties of cobalt oxide in the spinel structure

被引:285
作者
Chen, Jia [1 ]
Wu, Xifan [2 ,3 ]
Selloni, Annabella [1 ]
机构
[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
[2] Temple Univ, Dept Phys, Temple Mat Inst, Philadelphia, PA 19122 USA
[3] Temple Univ, Inst Computat Mol Sci, Philadelphia, PA 19122 USA
关键词
DENSITY-FUNCTIONAL CALCULATIONS; CO3O4; PSEUDOPOTENTIALS; INSULATORS; TRANSITION; OXIDATION; EXCHANGE;
D O I
10.1103/PhysRevB.83.245204
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
The spinel cobalt oxide Co3O4 is a magnetic semiconductor containing cobalt ions in Co2+ and Co3+ oxidation states. We have studied the electronic, magnetic, and bonding properties of Co3O4 using density functional theory (DFT) at the Generalized Gradient Approximation (GGA), GGA + U, and PBE0 hybrid functional levels. The GGA correctly predicts Co3O4 to be a semiconductor but severely underestimates the band gap. The GGA + U band gap (1.96 eV) agrees well with the available experimental value (1.6 eV), whereas the band gap obtained using the PBE0 hybrid functional (3.42 eV) is strongly overestimated. All the employed exchange-correlation functionals predict three unpaired d electrons on the Co2+ ions, in agreement with crystal field theory, but the values of the magnetic moments given by GGA + U and PBE0 are in closer agreement with the experiment than the GGA value, indicating a better description of the cobalt localized d states. Bonding properties are studied by means of maximally localized Wannier functions (MLWFs). We find d-type MLWFs on the cobalt ions, as well as Wannier functions with the character of sp(3)d bonds between cobalt and oxygen ions. Such hybridized bonding states indicate the presence of a small covalent component in the primarily ionic bonding mechanism of this compound.
引用
收藏
页数:7
相关论文
共 46 条
[1]   Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].
Adamo, C ;
Barone, V .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170
[2]   BAND THEORY AND MOTT INSULATORS - HUBBARD-U INSTEAD OF STONER-I [J].
ANISIMOV, VI ;
ZAANEN, J ;
ANDERSEN, OK .
PHYSICAL REVIEW B, 1991, 44 (03) :943-954
[3]  
[Anonymous], 2003, Highlight Mon. PsiK Newsl
[4]   A NEW MIXING OF HARTREE-FOCK AND LOCAL DENSITY-FUNCTIONAL THEORIES [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1372-1377
[5]   Order-by-disorder and spiral spin-liquid in frustrated diamond-lattice antiferromagnets [J].
Bergman, Doron ;
Alicea, Jason ;
Gull, Emanuel ;
Trebst, Simon ;
Balents, Leon .
NATURE PHYSICS, 2007, 3 (07) :487-491
[6]   Linear response approach to the calculation of the effective interaction parameters in the LDA+U method [J].
Cococcioni, M ;
de Gironcoli, S .
PHYSICAL REVIEW B, 2005, 71 (03)
[7]   Insights into current limitations of density functional theory [J].
Cohen, Aron J. ;
Mori-Sanchez, Paula ;
Yang, Weitao .
SCIENCE, 2008, 321 (5890) :792-794
[8]   Formation of the cerium orthovanadate CeVO4: DFT+U study [J].
Da Silva, Juarez L. F. ;
Ganduglia-Pirovano, M. Veronica ;
Sauer, Joachim .
PHYSICAL REVIEW B, 2007, 76 (12)
[9]   QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials [J].
Giannozzi, Paolo ;
Baroni, Stefano ;
Bonini, Nicola ;
Calandra, Matteo ;
Car, Roberto ;
Cavazzoni, Carlo ;
Ceresoli, Davide ;
Chiarotti, Guido L. ;
Cococcioni, Matteo ;
Dabo, Ismaila ;
Dal Corso, Andrea ;
de Gironcoli, Stefano ;
Fabris, Stefano ;
Fratesi, Guido ;
Gebauer, Ralph ;
Gerstmann, Uwe ;
Gougoussis, Christos ;
Kokalj, Anton ;
Lazzeri, Michele ;
Martin-Samos, Layla ;
Marzari, Nicola ;
Mauri, Francesco ;
Mazzarello, Riccardo ;
Paolini, Stefano ;
Pasquarello, Alfredo ;
Paulatto, Lorenzo ;
Sbraccia, Carlo ;
Scandolo, Sandro ;
Sclauzero, Gabriele ;
Seitsonen, Ari P. ;
Smogunov, Alexander ;
Umari, Paolo ;
Wentzcovitch, Renata M. .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2009, 21 (39)
[10]   THEORY OF IONIC ORDERING, CRYSTAL DISTORTION, AND MAGNETIC EXCHANGE DUE TO COVALENT FORCES IN SPINELS [J].
GOODENOUGH, JB ;
LOEB, AL .
PHYSICAL REVIEW, 1955, 98 (02) :391-408