Structural and electronic properties of (TiO2)10 clusters with impurities: A density functional theory investigation

被引:8
作者
Aguilera-del-Toro, R. H. [1 ,2 ]
Aguilera-Granja, F. [2 ]
Vogel, E. E. [3 ,4 ]
机构
[1] Univ Valladolid, Dept Fis Teor Atom & Opt, Valladolid, Spain
[2] Univ Autonoma San Luis Potosi, Inst Fis, San Luis Potosi, Mexico
[3] Univ la Frontera, Dept Ciencias Fis, Temuco, Chile
[4] Ctr Dev Nanosci & Nanotechnol CEDENNA, Santiago 9170124, Chile
关键词
DFT calculations; Structure; Electronic properties; Energetic properties; Impurities; DOPED TIO2 RUTILE; 1ST-PRINCIPLES CALCULATIONS; MODIFICATION MECHANISM; OPTICAL-PROPERTIES; DFT; CR; OS;
D O I
10.1016/j.jpcs.2019.109107
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report the structural, energetics, and electronic properties of free-standing binary clusters (TiO2)(10) with substitutional metallic and non-metallic impurities. The selected (TiO2)(10) cluster has tetrahedral symmetry and is the putative low energy structure for this size. The substitutional impurity can be located at a vertex (4 sites) or at an edge (6 sites). The former has a binding energy only 0.03 eV/atom less than the latter, so they can be considered as almost degenerate. A total of 28 impurities are considered in the present report. We study the edge substitutional place since this environment is very similar to the corresponding one in the bulk, which makes these system a possible model for the bulk-like structures. Another advantage of the cluster considered here is that its energy gap is as large as the one presented in the bulk phases (anatase and rutile). This system allows us to mimic the bulk behavior without the use of intrasite Coulomb corrections (U) usually applied to the 3d orbital electrons of Ti atoms U-d and 2p orbital electrons of the O atoms U-p; they are generally applied as parameters to fit the real energy gap observed in bulk (TiO2) systems. We show results for the formation energies, energy gaps and magnetism suggesting a way to control the band gap by means of the use of the appropriate impurity used in the substitution.
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页数:9
相关论文
共 38 条
[1]   New structural and electronic properties of (TiO2)10 [J].
Aguilera-Granja, F. ;
Vega, A. ;
Balbas, L. C. .
JOURNAL OF CHEMICAL PHYSICS, 2016, 144 (23)
[2]   Structural and magnetic properties of X12Y (X, Y=Fe, Co, Ni, Ru, Rh, Pd, and Pt) nanoalloys [J].
Aguilera-Granja, F. ;
Longo, R. C. ;
Gallego, L. J. ;
Vega, A. .
JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (18)
[3]   Substitutional 4d and 5d impurities in graphene [J].
Alonso-Lanza, Tomas ;
Ayuela, Andres ;
Aguilera-Granja, Faustino .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2016, 18 (31) :21913-21920
[4]   Ab initio study of neutral (TiO2)n clusters and their interactions with water and transition metal atoms [J].
Cakir, D. ;
Gulseren, O. .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2012, 24 (30)
[5]   Photoinduced reactivity of titanium dioxide [J].
Carp, O ;
Huisman, CL ;
Reller, A .
PROGRESS IN SOLID STATE CHEMISTRY, 2004, 32 (1-2) :33-177
[6]   A DFT study on modification mechanism of (N, S) interstitial co-doped rutile TiO2 [J].
Chen, Hao ;
Li, Xuechao ;
Wan, Rundong ;
Kao-Walter, Sharon ;
Lei, Ying ;
Leng, Chongyan .
CHEMICAL PHYSICS LETTERS, 2018, 695 :8-18
[7]   A DFT study of the electronic structures and optical properties of (Cr, C) co-doped rutile TiO2 [J].
Chen, Hao ;
Li, Xuechao ;
Wan, Rundong ;
Kao-Walter, Sharon ;
Lei, Ying .
CHEMICAL PHYSICS, 2018, 501 :60-67
[8]   Molecular and Dissociative Adsorption of Water on (TiO2)n Clusters, n=1-4 [J].
Chen, Mingang ;
Straatsma, Tjerk P. ;
Dixon, David A. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2015, 119 (46) :11406-11421
[9]  
Chul-Ko K., 2016, PHYS CHEM CHEM PHYS, V18, P12357
[10]   Formation of singlet molecular oxygen associated with the formation of superoxide radicals in aqueous suspensions of TiO2 photocatalysts [J].
Daimon, Toshihiro ;
Hirakawa, Tsutomu ;
Kitazawa, Masahiro ;
Suetake, Junya ;
Nosaka, Yoshio .
APPLIED CATALYSIS A-GENERAL, 2008, 340 (02) :169-175