0/&'0./+*1&23%&4,*#'*&seshadri/20180620-oxides-tutorial.pdfjun 20, 2018...
TRANSCRIPT
![Page 1: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/1.jpg)
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![Page 2: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/2.jpg)
This lecture
1. Brief description of oxide crystal structures (simple and complex)
a. Ionic radii and Pauling’s rulesb. Electrostatic valencec. Bond valence, and bond valence sums
Why do certain combinations of atoms take on specific structures?
2. Counting electrons and simple electronic structures (largely avoiding transition metals)
3. Trends in the transition metals
![Page 3: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/3.jpg)
My bookshelf
H. D. Megaw
O. Muller & R. Roy
I. D. Brown
B. G. Hyde &S. Andersson
![Page 4: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/4.jpg)
Software: ICSD + VESTA
Momma , Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data, J. Appl. Cryst. 44 (2011) 1272–1276. [doi:10.1107/S0021889811038970]
![Page 5: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/5.jpg)
Crystal structures of simple oxides [containing a single cation site]
![Page 6: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/6.jpg)
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![Page 9: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/9.jpg)
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![Page 11: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/11.jpg)
Oxides versus sulfides: TiS2
2H–TiS2
van der Waals gap (unlikely in oxides or fluorides, but occurs frequently in hydroxides)
This is the CdI2 structure.
![Page 12: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/12.jpg)
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![Page 13: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/13.jpg)
Shannon-Prewitt effective ionic radii
Radii assigned by systematically examining cation-anion pairs in oxides, fluorides etc.
May not work for other kinds of compounds
Be sensitive to coordination number and spin state
www.mrl.ucsb.edu/~seshadri/Periodic/index.html
![Page 14: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/14.jpg)
Ionic radii and Pauling’s first rule (the radius ratio rule)
In brief: The cation-anion distance is the sum of cation and anion radii, and the number of anions around a cation (the coordination number) is a function of the radius ratio. Exemplified by AO2 compounds below. MRR is the mimimum radius ratio.
Pauling, The Nature of the Chemical Bond, 3rd Edn.Cornell University Press, Ithaca 1960
Compound rC (A) rC + rO (A) rC/rO Coordination MRR
CO2 �0.19(?) 1.16 (exp.) ? 2
SiO2 0.26 1.61 0.19 4 0.225
TiO2 0.605 1.955 0.45 6 0.414
CeO2 0.97 2.32 0.72 8 0.732
![Page 15: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/15.jpg)
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![Page 16: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/16.jpg)
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![Page 17: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/17.jpg)
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![Page 18: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/18.jpg)
Electrostatic valence and bond valence: Parameters for Mn
Mn 2 O -2 1.790 0.37 aMn 2 O -2 1.765 0.37 jMn 2 S -2 2.22 0.37 eMn 2 F -1 1.698 0.37 aMn 2 Cl -1 2.133 0.37 aMn 2 Br -1 2.34 0.37 eMn 2 I -2 2.52 0.37 eMn 2 N -3 1.849 0.37 jMn 2 N -3 1.65 0.35 eMn 3 O -2 1.760 0.37 aMn 3 O -2 1.732 0.37 jMn 3 F -1 1.66 0.37 bMn 3 Cl -1 2.14 0.37 bMn 3 N -3 1.837 0.37 jMn 4 O -2 1.753 0.37 aMn 4 O -2 1.750 0.37 jMn 4 F -1 1.71 0.37 bMn 4 F -1 1.63 0.37 eMn 4 Cl -1 2.13 0.37 bMn 4 N -3 1.822 0.37 jMn 6 O -2 1.79 0.37 eMn 7 O -2 1.827 0.37 eMn 7 O -2 1.79 0.37 bMn 7 F -1 1.72 0.37 bMn 7 Cl -1 2.17 0.37 b
bvsparm.cif
Brown, Shannon, Empirical bond-strength-bond-length curves for oxides, Acta Cryst. A 29 (1973) 266–281
![Page 19: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/19.jpg)
Crystal structures of some complex oxides [containing two or more cation sites]
![Page 20: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/20.jpg)
The major ternary structural families (Muller and Roy, page 3, redrawn and modified)
A3BX5
Ternary structural families
others
A2BX4
ABX4
ABX3
CaCO3
Perovskite
Hexagonal ABX3 (eg. BaNiO3 in the CsCrBr3 structure)
Pyroxenes and related structures (eg. diopside CaMgSi2O6)
Corundum and related structures (eg. ilmenite FeTiO3)
Zircon (ZrSiO4)
Scheelite (CaWO4)
Barite (BaSO4)
Ordered SiO2 derivatives
Ordered rutile derivatives
K2NiF4 (m = 1 Ruddlesden-Popper)
b–K2SO4
Olivine (Mg2SiO4 and for eg. LiFePO4)
Spinel (MgAl2O4)
CaFe2O4
Phenacite (Be2SiO4)
ABX2 (eg. LiCoO2 and CuFeO2)
A2B2X7 (eg. pyrochloreY2Ti2O7)
A2BX5
A2BX6
not listed by Muller and Roy
Will discuss compounds in highlighted boxes: Characterized by dense connectivity.
![Page 21: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/21.jpg)
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![Page 23: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/23.jpg)
Ordered double perovskites (elpasolites)
Ba2MgWO6 Ca2MgWO6
Rock-salt like ordering of dissimilar octahedra. Space group same as rock-salt: Fm–3m
Smaller A-ions associated with tilting as in simple perovskites.
![Page 24: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/24.jpg)
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![Page 25: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/25.jpg)
Hexagonal ABO3 structures
BaNiO3 LiNbO3 (ferroelectric R3c)
Ferroelectric YMnO3 (“YAlO3”)
Unusual 5-fold coordination (trigonalbibyramid) of MnO5
![Page 26: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/26.jpg)
Ordered rutiles (the trirutile)
CoTa2O6: 3×TiO2 = Ti3O6; 3×Ti4+ = Co2+ + 2×Ta5+
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Sc Ti V CrMn
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Rh Ag Cd Sn
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Al
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ions on the B site
A,B Jahn-Teller active
A,B DiamagneticCo II High single-ion anisotropy
Spinel AB2O4
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Some ABO2 structures: Highly dense in-plane, and frequently metallic
LiCoO2 (ordered rock-salt) 3R–CuFeO2 (delafossite)
111-ordered with alternating octahedral LiO6 and CoO6 stacking
BO2 (CdI2) slabs separated by two-coordinate atoms, usually Cu+ and Ag+. Also unusually, Pd1+ and Pt1+.
![Page 32: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/32.jpg)
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Counting electrons
![Page 34: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/34.jpg)
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Some “real” electronic structures: MoS2 a d2 semiconductor
MoS6 prisms allow a crystal-field gap between the filled dz2 and the rest of the d
states. Structure matters !
![Page 37: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/37.jpg)
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Transition metal compounds: Trends in energetics and insulator-to-metal transitions
![Page 41: 0/&'0./+*1&23%&4,*#'*&seshadri/20180620-Oxides-Tutorial.pdfJun 20, 2018 · LiFePO 4) Spinel (MgAl 2O 4) CaFe 2O 4 Phenacite(Be 2SiO 4) ABX 2 (eg. LiCoO 2 and CuFeO 2) A 2B 2X 7 (eg](https://reader033.vdocuments.site/reader033/viewer/2022052101/603ae3d8ae108e0e763257ad/html5/thumbnails/41.jpg)
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