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SS 2002
Introduction
Textbooks: Introduction to Solid State Chemistry (English) 1. Doughlas, McDaniel, Alexander, Concepts and Models of Inorganic Chemistry, Wiley, 1992 2. Shriver, Atkins, Inorganic Chemistry (3rd ed, 1999) W.H. Freeman and Company (Chs. 3, 18 ...) 3. L. Smart, E. Moore, Solid State Chemistry, 2nd Ed. Chapman & Hall, London, 1995 4. P.A. Cox, The Electronic Structure and Chemistry of Solids, Oxford University Press, 1987 5. U. Mller, Inorganic Structural Chemistry Wiley, Chichester, 1993 6. A.R. West, Solid State Chemistry and its Applications Wiley, New York, 1984
Tremel: Solid State Chemistry
Introduction
Textbooks II: Solid State Chemistry (German) 1. E. Riedel: Moderne Anorganische Chemie, de Gruyter 1999, S. 329 523 ( Festkrperchemie ) 2. L. Smart, E. Moore: Einfhrung in die Festkrperchemie, Vieweg 1997 3. A.R. West: Grundlagen der Festkrperchemie, VCH 1992 4. U. Mller: Anorganische Strukturchemie Teubner Studienbcher 1991 5. E. Riedel: Moderne Anorganische Chemie de Gruyter 1999, S. 329 523 ( Festkrperchemie )
Covalent solids
conducting
aromatic
aliphatic
What is special about the solid compared to molecules? Molecules such as HCl, C6H6 or C60 are identical and stochiometric Solid state compounds may be nonstochiometric Example: FeO is really Fe1-xO ! Fe1-xO FeO1+x Other examples: NaxWO3, WO3-x
What is special about the solid compared to molecules? Solid solutions: composition determines the properties Examples: Doped semiconductors n-Si/p-Si LASERs Al2O3(Cr3+) Dielectrics Ba1-xCaxTiO3 Pigments (TiO2-xFx, CdS/CdSe) Steel (Fe/C)
mailbox yellow blue NaCl
What is special about the solid compared to molecules? Periodicity leads to Order-disorder effects (e.g. in intermetallic compounds)
FeAl or CuZn
Localization-delocalization of charge carriers (metallic conductivity, polarons ...) Collective properties such as magnetism (e.g. Fe, Co, NiO, CoFe2O4)
What is special about the solid compared to molecules? Extended structures no localized chemical reactivity low mobility of constituents large activation energies for reactions high reaction temperatures/thermodynamic control phase diagrams important for chemical reactions experiments under extreme physical conditions: very high pressures and temperatures Description in terms of structure types Packing/coordination polyhedra vs. molecular units
CRYSTAL STRUCTURE
The periodic arrangement of atoms in the crystal. It can be described by associating with each lattice point a group of atoms called the MOTIF (BASIS)
UNIT CELL
The smallest component of the crystal, which when stacked together with pure translational repetition reproduces the whole crystal, Primitive (P)unit cells contain only a single lattice point Don't mix up atoms with lattice points Lattice points are infinitesimal points in space Atoms are physical objects Lattice Points do not necessarily lie at the centre of atoms
Tremel: Solid State Chemistry
Close packing
1926 Goldschmidt proposed atoms could be considered as packing in solids as hard spheres
This reduces the problem of examining the packing of like atoms to that of examining the most efficient packing of any spherical object - e.g. have you noticed how oranges are most effectively packed in displays at your local shop?
A second layer of spheres is placed in the indentations left by the first layer space is trapped between the layers that is not filled by the spheres TWO different types of HOLES (INTERSTITIAL sites) are left OCTAHEDRAL (O) holes with 6 nearest sphere neighbours TETRAHEDRAL (T) holes with 4 nearest sphere neighbours
Tremel: Solid State Chemistry
A second layer of spheres is placed in the indentations left by the first layer
(polytypism !!)
ABABAB.... repeat gives Hexagonal Close-Packing (HCP) Unit cell showing the full symmetry of the arrangement is Hexagonal 2 atoms in the unit cell: (0, 0, 0) (2/3, 1/3, 1/2)
Tremel: Solid State Chemistry
ABCABC.... repeat gives Cubic Close-Packing (CCP) Unit cell showing the full symmetry of the arrangement is Face-Centred Cubic 4 atoms in the unit cell: (0, 0, 0) (0, 1/2, 1/2) (1/2, 0, 1/2) (1/2, 1/2, 0)
Tremel: Solid State Chemistry
68% of space is occupied Coordination Number ? 8 Nearest Neighbours at 1 2 3 a =0.87a 6 Next-Nearest Neighbours at 1a