Mr. T.
ZARIMA
Room 30 Curriculum
[email protected]
Cell: +263778769859
WhatsApp: +263778769859
HCH210: Solid state chemistry
Solid state chemistry - the study of synthesis,
structure, bonding, reactivity, and physical
properties of solids.
Course outline
Content
Crystals: synthesis and characterization (18 lectures)
• Symmetry elements and operations
• Point groups and their determination
• Stereographic representation
• Crystal systems and space groups
• Lattices: metallic, ionic and giant molecule
• Theory of X-ray structure determination: Bragg’s law, reflections, systematic
absences, scattering factors
• Single crystal X-ray diffraction: structure factors, the phase problem.
Solid state chemistry (18 lectures)
• Solid state synthesis of crystals
• Bonding in solids and electronic properties
• Band Theory of solids, Conductors, insulators and semiconductors
• Defects and non-stoichiometry compounds
• X-Ray diffraction
Practicals (12hrs)
• Preparation of transition metal compounds
• Investigation of chemical and physical properties of transition metal
complexes
Assessments
• One assignment from section A and another one from section B
• One test from section A and another from section B
References
• Smart, L. E., Moore, E. A., Solid State Chemistry: An Introduction, 3rd
Edition, Taylor and Francis, 2005.
• Atkins, P., de Paula, J., Physical Chemistry, 8th Edition, Oxford University
Press, 2006.
• West, A. R., Basic Solid State Chemistry, 2nd Edition, John Wiley & Sons,
1999.
Concept of symmetry in
molecules
by
Mr T. ZARIMA
Symmetry and group theory
• Symmetry is the quality of being made up of exactly similar parts facing
each other or around an axis.
• Nature is full of objects that exhibit varying degrees of symmetry
• Objects living or non-living (organic or inorganic) are made up of molecules
• Symmetry is a physical property of these molecules and is quite intimate
with their geometry
• Molecules are finite and concrete particles in all states of aggregation,
consisting of defined number of atoms
• The symmetry relationships in the molecular structure provide the basis for
a mathematical theory, called group theory
• The mathematics of group theory is predominantly algebra
• Since all molecules are certain geometrical entities, the group theory
dealing with such molecules is also called as the “algebra of geometry”.
Why study symmetry?
• Symmetry concepts are of capital importance in all branches of chemistry
• By analysing the symmetry of molecules, we can:
– Predict infrared spectra
– Describe orbitals used in bonding
– Predict optical activity
– Interpret electronic spectra
– And study a number of additional molecular properties
Symmetry of what?
• In crystallography (the language of describing crystals) when we talk of
Symmetry; the natural question which arises is: Symmetry of What?
• The symmetry under consideration could be of one the following entities:
Lattice,
Crystal,
Motif (molecule), or
Unit cell.
(these are distinct and should not be confused with one another!)
• When the symmetry is normally used, it is the symmetry of the crystal being
referred to.
Symmetry
• Point symmetry-is the symmetry possessed by a single molecule or object
that describes the repetition of identical parts of the molecule or object
• A symmetry element is an imaginary geometrical construct about which a
symmetry operation is performed.
– There are five types of symmetry elements: rotational axis of symmetry (Cn),
plane of symmetry or mirror (σ), improper rotational axis of symmetry (Sn),
inversion centre or centre of symmetry (i), and identity element (E).
Symmetry operations
• A symmetry operation is a movement of an object about a symmetry
element such that the object's orientation and position before and after the
operation are indistinguishable.
– If a symmetry operation yields a molecule that can be distinguished from the
original in any way, that operation is not a symmetry operation for the molecule.
– A symmetry operation carries every point in the object into an equivalent point or
the identical point.
• The identity operation (E) causes no change in the molecule. It is included
for mathematical completeness.
– An identity operation is characteristic of every molecule, even if it has no other symmetry.
H
C
F Br
Cl
• There are two types of rotational axes:
– Principal rotational axis, Cn(n=highest): This is also called as the highest-fold rotational axis.
– Simple or secondary rotational axes: These may be often C2 axes, and the number of such
axes present is always equal to n, the order of principal axis, Cn.
• An example of a molecule having a threefold (C3) axis is CHCl3. The rotation
is coincident with the C-H bond axis, and the rotation angle is 360˚/3 = 120˚.
– Two C3 operations may be performed to give a new rotation of 240˚. The resulting operation
is designated C32 and is also a symmetry operation of the molecule. Three successive C 3
operations are the same as the identity operation (C 32 ≡ E)
360 0
Symbol for 2-fold axis n
=180 n=2 2-fold rotation axis
Then the operation of the 2-fold
leaves two points
Symbol for 3-fold axis
=120 n=3 3-fold rotation axis
=90 n=4 4-fold rotation axis
=60 n=6 6-fold rotation axis
• Reflection operation (mirror) (σ) –molecule contains a mirror plane.
– The reflection operation exchanges left and right, as if each point had moved
perpendicularly through the plane to a position exactly as far from the plane as when it
started.
– Linear objects, such as a round wooden pencil, or molecules, such as acetylene and carbon
dioxide, have an infinite number of mirror planes that include the centre line of the object.
• σh(horizontal): plane perpendicular to principal axis
• σd(dihedral), σv(vertical): plane colinear with principal axis
– σv: Vertical, parallel to principal axis
– σd: σ parallel to Cn and bisecting two C2' axes
• Inversion operation-Each point moves through the centre of the molecule to
a position opposite the original position and as far from the central point as
where it started.
• Ethane in the staggered conformation is a good example
• Methane and other tetrahedral molecules lack inversion symmetry.
• Ru(CO)6
• A rotary-reflection operation (Sn), or improper rotation, requires rotation of
360˚/n, followed by reflection through a plane perpendicular to the axis of
rotation.
– In methane, a line through the carbon atom and bisecting the angle between two hydrogen
atoms on each side is an S4 axis. There are 3 such lines, for a total of three S 4 axes; a
tetrahedron has 6 edges, and each of these axes bisects a pair of opposite edges.
– The operation requires a 90˚ rotation of the molecule, followed by reflection through the
plane perpendicular to the axis of rotation.
• Two Sn operations in succession generate a Cn/2 operation. For example two
S4 operations are equivalent to a C2.
• Molecules sometimes have an Sn axis coincident with a Cn axis. Snowflakes
have S2(≡ i), S3, and S6 axes coincident with the C6 axis.
• Molecules may also have S2n axes coincident with Cn; methane is an
example, with S4 axes coincident with C2 axes, as shown on the next slide.
• Note that an S2 operation is the same as an inversion, and an S1 operation
is the same as a reflection plane.
