What is Solid State Chemistry ?

Most of the chemical elements and their compounds are solids at room temperature

Na (metallic) Rock Salt (Ionic) Perovskite (minerals)

Polyacetilene (organic) Molecular 2

 The Importance of solids
Many of the characteristic properties of solids depend directly on the behavior of the electrons
in them:
PES
insulator XRD
semiconductor XAS
conductor
XES
Electrical conduction
Optical properties:

Para-
Ferro-
Antiferro-
magnetism
Magnetic Properties
Surface properties 3
Nitrogenase metal cluster
Rees and coworkers (2002) reported a refinement of nitrogenase to 1.16 resolution.

N2 + 8H+ +8e- 16MgATP 2NH3 +H2 + 16MgADP + 16Pi

4
 Our Pursuit of the M(SR)3 fragment

O
O N(His215)
Mo
S S
M S
S S S

Fe
Fe Fe

X
X
S S S

Fe Fe Fe

S S S

Fe

S(protein)

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co[FeMo] Bioinspired models complexes

Chatt, J. J. Cummins, C. C. Schrock, R. R.

Chem. Soc., Dalton. Trans. 1977, 1852. Science 1995, 268, 861. Inorg. Chem. 2003, 42, 796

Peters, J. C. Peters, J. C.
Peters, J. C.
JACS 2003, 125, 322. PNAS 2013, 110, 15899. 6
Inorg. Chem. 2009, 48, 2507.
7
The Importance of solids

Many of the applications of solids depend on these electronic properties:

integrated circuits
lasers

recording tape

solar energy converters

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The Importance of solids

The wide diversity of electronic properties of solids reflects an equally wide range of
chemical-bonding interactions

Some aspects of electronic structure are certainly unique to solids, and these will involved
concepts which are rather unfamiliar to chemist.
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The Importance of solids

Most solids form crystals, in which the atoms or molecules are packed in regular Arrays.

Esmerald Quartz Epidote Glass

The traditional methods for treating the electronic structure of a solid depend heavily on
crystalline order, and break down when faced with highly disordered materials
 Chemical classification of solids
Solids are most conveniently classified in terms of types of force which hold the atoms
together.
Class Example
Xe
N2
Molecular Solids
C6H6
HgCl2
NaCl
Ionic Solids MgO
CaF2
C(diamond)
P
Covalent Solids
SiO2
GeAs
Na
Metallic Solids Fe
Cu
Chemical classification of solids: Molecular solids
Atoms or molecules : weak van der waals forces.

London dispersion force

van der waals forces

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Chemical classification of solids: Molecular solids
London dispersion force is a temporary attractive force that results when the electrons in two
adjacent atoms occupy positions that make the atoms form temporary dipoles.

Electronic excitation energy Distance

Electronic polarizability

Since the dispersion force in non-directional and falls off rapidly with distance, the main
structural driving force is the packing of molecules as closely together as possible 13
Chemical classification of solids: Molecular solids

London forces are the attractive forces that cause nonpolar substances to condense to liquids and
to freeze into solids when the temperature is lowered sufficiently.

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Chemical classification of solids: Molecular solids

Thus fairly symmetrical

groups such as atomic
xenon and molecular
nitrogen have close-
packed structures like
those of metal.

With molecules as benzene that are far from spherical, the close-packing in the structure is not
sot obvious

Repulsive H---H
interaction

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Chemical classification of solids: Molecular solids

Polar molecules have more directional forces: for example the electrostatic interaction between
permanent dipoles. Hydrogen Bond

B(OH)3

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Chemical classification of solids: Ionic solids
the bonding is assumed to arise from the electrostatic attraction between ions. The energy of
interaction between two ions, with charges z1 y z2, is given by Coulomb law:

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Chemical classification of solids: Ionic solids
Chemical classification of solids: Ionic solids

The coulomb force favours structures where each ion is sorrounded by ones of opposite
charge.

It would seem that the lowest energy structures would be the ones with the largest madelung
constanst which are generally those with highest possible coordination number
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Chemical classification of solids: Covalent solids
Giant covalent lattices Atoms are held together by covalent bonds

Bond energy and length of the C-C bond in diamond alkanes.

The structures of covalent lattices are also determined by the same factors as those in
molecules

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Chemical classification of solids: Covalent solids
The structures of covalent lattices are also determined by the same factors as those in
molecules

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Chemical classification of solids: Covalent solids

N N O O
Graphite Diamond Nitrogen Oxygen

Carbon

Si, Ge and Sn Group V Se S 22

Chemical classification of solids: Covalent solids

The so-called 8-N rule relates the coordination in the solid to the group number N, and is a
reflection of the structures found in many small covalent molecules, such as hydrides.

2s 2p

3s 3p

The progressive lowering of coordination number occurs as the number of electron increases
beyond that of the available atomic orbitals
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Chemical classification of solids: Metallic solids

Metals are characterized by a delocalized sharing of electrons between many atoms.

In general, metallic structures are formed by elements with a deficiency of electrons, relative
to the number of bonding orbitals.

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Chemical classification of solids: Metallic solids

Metals tend to adopt close-packed or nearly close-packed structures:

factors which determine the structure of metal, are quite complicated. To discuss these requires
the use of band theory
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Chemical classification of solids: More complex solids

Bonding type Example

Intermediate ionic covalent CdS, TiO2, CsAu
Intermediate ionic covalent + van der waals CdI2
Ionic, Metallic NbO, TiO
Ionic, metallic, van der waals ZrCl
Ionic, covalent, metallic K2Pt(CN)4Br0.3.3H2O)
Covalent, metallic, van der waals graphite
Ionic, covalent, metallic, van der waals TTF:TCNQ

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Chemical classification of solids: More complex solids

Cd E = 1,69
S E = 2,58 Ionic-covalent
CdS

TiO2

ionic model: useful in discussing the electronic structure of compounds such as this, it is
certain that the ionic description does not give a true picture of the charge distribution.

CsAu Cs+Au-

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Sometimes intermediated ionic-covalent bonding is combined with other interactions.

CdI2 MoS2

NbO
ZrCl
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Chemical classification of solids: More complex solids

Delocalized metallic bonding may even occur in predominantly molecular solid, such as
compound TTF:TCNQ

K2Pt(CN)4Br0.3.3H2O KCP
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 Crystallography and Structure of
the Elements
Crystals: very long range periodic order of the atoms degree of
macroscopic symmetry.

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Crystallography and Structure of the Elements

Not all inorganic solids are crystalline, glass being a prominent exception, and most liquids

crystal Liquid-crystal Liquid

Because the realm of inorganic solids consists mainly of crystalline, rather than amorphous,
substances we can adduce that maximum thermodynamic stability is achieved by the creation
of the spatial periodicity of the atoms
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 ~ 24 % by mass of the
Earths crust is silicon
(Mg+2, Fe+2)2SiO4

Al2SiO4F2(OH)2

The element is gray, metallic looking

it is not classified as a metal because
it has a low electrical conductivity

Be3Al2(SiO3)6
Crystallography and Structure of the Elements

Johannes Kepler (1571-1630) In 1611 Kepler wrote Six-cornered Snowflake (Latin

title Strena Seu de Nive Sexangula) Why do single snowflakes, before they become
entangled with other snowflakes, always fall with six corners? ..
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 Symmetry
The geometric relationship between the planar faces determined the macroscopic symmetry by
which crystals were first grouped and cataloged

Niels Stensen, (1638-1686) who became professor of anatomy at the University of Padua in
Italy. In Stensens work De Solido Intra Solidum he observed for the first time the
fundamental crystallographic Law of the Constancy of Interfacial Angles. 34
Symmetry

The degree and type of symmetry possessed by any object is determined by certain symmetry
operations, e.g., rotation, translation, and reflection.

4 3 2 1
Rotation of a perfect sphere about any of the infinite number
of axes passing through its center leaves the object unchanged
with reference to any arbitrary set of external coordinates.

Rotation-Inversion

Plane of reflection Translation

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Symmetry

Although objects themselves may appear to have 5-fold, 7-fold, 8-fold, or higher-fold rotation
axes, these are not possible in crystals.

3 4 6

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5 7 8
 Three fourfold Four threefold
rotation axes rotation axes

six twofold
rotation axes

one should not conclude from this that all cubic structures are described by a
simple cube possessing all possible symmetry elements
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Spinal AB2O4

Oxygen

B-Octahedral sites

A-Tatrahedral sites

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