Electronic and magnetic structure of Fe3S4: GGA+U investigation

被引:71
作者
Devey, A. J. [1 ]
Grau-Crespo, R. [1 ]
de Leeuw, N. H. [1 ]
机构
[1] UCL, Dept Chem, London WC1H 0AJ, England
基金
英国工程与自然科学研究理事会;
关键词
ab initio calculations; density functional theory; electronic structure; energy gap; ferrimagnetic materials; Hubbard model; iron compounds; lattice constants; magnetic moments; magnetic structure; magnetic transitions; DENSITY-FUNCTIONAL THEORY; INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; IRON; GREIGITE; TRANSITION; MACKINAWITE; MOSSBAUER; EXCHANGE; SPECTRA;
D O I
10.1103/PhysRevB.79.195126
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
The electronic and magnetic behavior of the iron sulphide mineral greigite (Fe3S4) is studied using ab initio density-functional theory in the generalized gradient approximation (GGA) with the on-site Hubbard U-eff parameter (GGA+U). The effect of the Hubbard correction is investigated and is found to be a necessary requirement for the accurate description of both the unit cell structure and the magnetic moment. A ferrimagnetic normal-spinel structure is found when U-eff=0 eV, while for all values of U-eff>0 eV an inverse spinel structure is predicted, in agreement with experiment. For low values of U-eff (0 < U-eff < 4 eV) the predicted electronic structure corresponds to that of a semimetal, with semimetallicity arising from electron hopping between ferric and ferrous Fe on octahedral sites. For values of U-eff >= 4 eV the S atoms are found to oxidize the ferrous octahedral sites Fe to the ferric state. To determine whether GGA+U predicts a stable monoclinic form of greigite arising from a Verwey-type low-temperature transition, analogous to that seen in magnetite, a monoclinic form of greigite is postulated. It is found that such a phase is stable, with an electronic band-gap opening up for values of U-eff >= 2 eV, but is energetically unfavorable when compared with the spinel phase for all U-eff values tested. It is argued that an accurate description of all the properties of greigite requires a U-eff value of approximately 1 eV.
引用
收藏
页数:7
相关论文
共 57 条
[1]   First-principles calculations of the electronic structure and spectra of strongly correlated systems: The LDA+U method [J].
Anisimov, VI ;
Aryasetiawan, F ;
Lichtenstein, AI .
JOURNAL OF PHYSICS-CONDENSED MATTER, 1997, 9 (04) :767-808
[2]   MAGNETIZATION AND EXCHANGE IN NONSTOICHIOMETRIC MAGNETITE [J].
ARAGON, R .
PHYSICAL REVIEW B, 1992, 46 (09) :5328-5333
[3]   PROPERTIES OF ATOMS IN MOLECULES - ATOMIC VOLUMES [J].
BADER, RFW ;
CARROLL, MT ;
CHEESEMAN, JR ;
CHANG, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (26) :7968-7979
[4]   PROJECTOR AUGMENTED-WAVE METHOD [J].
BLOCHL, PE .
PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979
[5]   Fundamental magnetic parameters from pure synthetic greigite (Fe3S4) [J].
Chang, Liao ;
Roberts, Andrew P. ;
Tang, Yan ;
Rainford, Brian D. ;
Muxworthy, Adrian R. ;
Chen, Qianwang .
JOURNAL OF GEOPHYSICAL RESEARCH-SOLID EARTH, 2008, 113 (B6)
[6]   MAGNETIC STRUCTURE OF SPINEL FE3S4 [J].
COEY, JMD ;
SPENDER, MR ;
MORRISH, AH .
SOLID STATE COMMUNICATIONS, 1970, 8 (20) :1605-&
[7]   Magnetic properties of hydrothermally synthesized greigite (F3S4) -: II.: High- and low-temperature characteristics [J].
Dekkers, MJ ;
Passier, HF ;
Schoonen, MAA .
GEOPHYSICAL JOURNAL INTERNATIONAL, 2000, 141 (03) :809-819
[8]   Combined density functional theory and interatomic potential study of the bulk and surface structures and properties of the iron sulfide mackinawite (FeS) [J].
Devey, A. J. ;
Grau-Crespo, R. ;
de Leeuw, N. H. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (29) :10960-10967
[9]   Electronic and magnetic properties of V-doped anatase TiO2 from first principles [J].
Du, Xiaosong ;
Li, Qunxiang ;
Su, Haibin ;
Yang, Jinlong .
PHYSICAL REVIEW B, 2006, 74 (23)
[10]   Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J].
Dudarev, SL ;
Botton, GA ;
Savrasov, SY ;
Humphreys, CJ ;
Sutton, AP .
PHYSICAL REVIEW B, 1998, 57 (03) :1505-1509