Lecture B3 A 1
Lecture B3 A 1
Lecture B3 A 1
1
Group Theory
Covalent Bond Theories
1.
VSEPR (valence shell electron pair repulsion model).
A set of empirical rules for predicting a molecular geometry using,
as input, a correct Lewis Dot representation.
2.
Valence Bond theory.
A more advanced description of orbitals in molecules. We emphasize
just one aspect of this theory: Hybrid atomic orbitals.
Works especially well for organic molecules.
1.
VSEPR (valence shell electron pair repulsion model).
A set of empirical rules for predicting a molecular geometry using,
as input, a correct Lewis Dot representation.
2.
Valence Bond theory.
A more advanced description of orbitals in molecules. We emphasize
just one aspect of this theory: Hybrid atomic orbitals.
Works especially well for organic molecules.
1.
VSEPR (valence shell electron pair repulsion model).
A set of empirical rules for predicting a molecular geometry using,
as input, a correct Lewis Dot representation.
Molecular Geometry
is described by
Group Theory!
Point Group Symmetry
Point group symmetry is an important property of molecules widely used in some branches of
chemistry: spectroscopy, quantum chemistry and crystallography.
An individual point group is represented by a set of symmetry “elements” or operations:
• E - the identity ( abbreviated to E, from the German 'Einheit' meaning Unity)
• Cn - rotation by 2π/n angle *
• σs - reflection plane
• σh - horizontal reflection plane (perpendicular to the principal axis) **
• σv - vertical reflection plane (contains the principal axis)
• σd - diagonal reflection plane (contains the principal axis and bisects the angle between two
C2 axes perpendicular to the principal axis)
• i - Center of symmetry or inversion center. A molecule has a center of symmetry when, for
any atom in the molecule, an identical atom exists diametrically opposite this center an equal
distance from it. There may or may not be an atom at the center.
• Sn - improper rotation (rotation by 2π/n angle and reflection in the plane perpendicular to the
axis)
* - n is an integer
** - principal axis is a Cn axis with the biggest n.
A molecule belongs to a symmetry point group if it is unchanged under all the symmetry
operations of this group.
1. Identity is indicated as E does nothing, has no effect
All molecules/objects possess the identity operation, i.e.,
possess E.
E has the same importance as the number 1 does in
multiplication (E is needed in order to define inverses).
H2O
2. n-Fold Rotations: Cn, where n is an integer
rotation by 360°/n about a particular axis defined as the n-fold
rotation axis.
C2 = 180° rotation, C3 = 120° rotation, C4 = 90° rotation, C5
= 72° rotation, C6 = 60° rotation, etc.
Rotation of H2O about the axis shown by 180° (C2) gives the
same molecule back.
Therefore H2O possess the C2 symmetry element.
H2O
3. Reflection: σs (the symmetry element is called a mirror plane
or plane of symmetry)
If reflection about a mirror plane gives the same molecule/
object back than there is a plane of symmetry (σs).
If plane contains the principle rotation axis (i.e., parallel), it is a
vertical plane (σv)
If plane is perpendicular to the principle rotation axis, it is a
horizontal plane (σh)
If plane is parallel to the principle rotation axis, but bisects
angle between 2 C2 axes, it is a diagonal plane (σd)
H2O possesses 2 σv mirror planes of symmetry because they
are both parallel to the principle rotation axis (C2)
4. Inversion: i (the element that corresponds to this operation is a
center of symmetry or inversion center)
The operation is to move every atom in the molecule in a straight
line through the inversion center to the opposite side of the
molecule.
Therefore XeF4 possesses an inversion center at the Xe atom.
XeF4
5. Improper Rotations: Sn
n-fold rotation followed by reflection through mirror plane
perpendicular to rotation axis
Note: n is always 3 or larger because S1 = s and S2 = i.
Ethane C2H6
S6 axis
An example: H2O
Symmetry elements
An example: H2O
Irreducible Representations
An example: H2O
Number of vibrations: 3N - 6 = 3
C2v
IR activity is denoted by x, y or z
Normal mode vibrations: 2 A1 + B2
An example: H2O
Number of vibrations: 3N - 6 = 3
C2v
Number of vibrations: 3N - 6 = 3
C2v
Number of vibrations: 3N - 6 = 3
ν1 vibration: 3657 cm-1
A1 symmetry, OH symmetric stretch
Both IR and Raman active.
An example: H2O
Number of vibrations: 3N - 6 = 3
Number of vibrations: 3N - 6 = 3
C2v
Seesaw Geometry
CO2
D∞h
PCl5
D3h
XeF4 D4h
CH4
Td
SF6
Oh