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Molecular Symmetry
MOLECULAR SYMMETRY
• Bundet Boekfa
• Chem Div, Faculty Lib Arts & Sci
• Kasetsart University Kamphaeng Saen Campus
Molecular Symmetry
(c) The groups Dn, Dnh, and Dnd
It process a horizontal mirror
plane. The planar trigonal BF3
molecule has the elements
E, C3, 3C2, and σh (with one C2
axis along each B-F bond), so
belongs to D3h .
Molecular Symmetry
(c) The groups Dn, Dnh, and Dnd
All homonuclear diatomic
molecules, such as N2, belong to the
group D∞h because all rotations
around the axis are symmetry
operations, as are end-to-end
rotation and end-to-end reflection; D
∞h is also the group of the linear OCO
and HCCH molecules and of a
uniform cylinder.Other examples of
Dnh molecules are shown in (9), (10),
and (11).
(b) The groups Cn, Cnv, and Cnh
Objects that in addition to the
identity and an n-fold principal
axis also have a horizontal mirror
plane σh belong to the groups Cnh.
An example is trans-CHCl=CHCl
(6), which has the elements E, C2,
and σh, so belongs to the group
C2h; the molecule B(OH)3 in the
conformation shown in (7) belongs
to the group C3h.
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Molecular Symmetry
(c) The groups Dn, Dnh, and Dnd
The C6H6 molecule has
the elements E, C6, 3C2,
3C2’, and σh together with
some others that these
elements imply, so it
belongs to so belong to
D6h.
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Molecular Symmetry
(c) The groups Dn, Dnh, and Dnd
A molecule belongs to the group Dnd
if in addition to the elements of Dn it
possesses n dihedral mirror planes
σd. The twisted, 90° allene (12)
belongs to D2d, and the staggered
conformation of ethane (13) belongs
to D3d.
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Molecular Symmetry Molecular Symmetry

(d) The groups Sn (e) The cubic groups

Molecules that have not been classified A number of very important molecules (e.g.
into one of the groups mentioned so CH4 and SF6) possess more than one
far, but that possess one Sn axis, principal axis. Most belong to the cubic
belong to the group Sn. An example is groups, and in particular to the tetrahedral
tetraphenylmethane, which belongs to groups T, Td and Th
the point group S4 (14). Molecules
belonging to Sn with n > 4 are rare.
Note that the group S2 is the same as
Ci, so such a molecule will already
have been classified as Ci.
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Molecular Symmetry Molecular Symmetry

(e) The cubic groups
(e) The cubic groups
The groups Td and Oh are the groups of the tetrahedron
(CH4) and the octahedron (SF6). If the object possesses
A few icosahedral (20-faced)
the rotational symmetry of the tetrahedron or the
molecules belonging to the
octahedron, but none of their planes of reflection, then
icosahedral group, the
boranes and it belongs to the simpler groups T or O.
buckminsterfullerene, C60 (15).

The group Th is based on T

but also contains a centre
9 of inversion. 10

Molecular Symmetry
(f) The full rotation group
The full rotation group, R3 (the 3
refers to rotation in three dimensions),
consists of an infinite number of rotation
axes with all possible values of n. A
sphere and an atom belong to R3, but
no molecule does. Exploring the
D5h consequences of R3 is a very
important way of applying symmetry
arguments to at atoms, and is an
alternative approach to the theory of
11 orbital angular momentum. 12

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Molecular Symmetry Molecular Symmetry

Some immediate consequences of symmetry Some immediate consequences of symmetry
Chirality A molecule may be chiral, and therefore
Polarity only molecules belonging
optically active, only if it does not
to the groups Cn , Cnv, and
possess an axis of improper rotation, Sn.
Cs may have a permanent
electric dipole moment

For Cn , Cnv, that dipole moment must lie along

the symmetry axis. Thus ozone,O3, which is
angular and belongs to the group C2V, may be
polar (and is), but carbon dioxide, CO2, which is
linear and belongs to the group D∞h, is not.
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Molecular Symmetry
Determining the Point Group
• A flowchart for determining the point group of a molecule
Some immediate consequences of symmetry Some immediate
มีแกน consequences
C (n>2) nof
มีแกน Csymmetry
n แกนที่ตงั ้ 2
มากกว่า 2 แกน ฉากกับแกนหลัก
Molecules with the same list of elements are Molecule Linear 2 Cns
n>2
Cn ? n C2 ? h ? Dnh
classified to the same group.
The groups C1, Ci and Cs (no rotational axis) Cnh h ?
The groups Cn, Cnv and Cnh (n-fold axis) Dh i? Cv
Cs ? n d ? Dnd
The groups Dn, Dnh, Dnd (n-fold axis and n
perpendicular C2s) Td i? Cnv n v ?
Dn
The groups Sn (n-fold improper axis) Ci i?

The cubic groups

Oh C5 ? S2n S2n ?
Tetrahedral groups (T, Td, Th) C1
Octahedral groups (O, Oh) Yes
Ih Cn No
Icosahedral groups (I)
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Molecular Symmetry
Applications to molecular orbital theory
and spectroscopy
Character tables and symmetry labels

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Character Table Representations and Characters

 Character Table is a table that characterizes the  All the operators can be written in the matrix form.
different symmetry types possible in the point group.  The matrix is called a representation of an operator.
 The entries in a complete character table are derived • C2v
by using the formal techniques of group theory.
• SO2 (px)
C2V (E, C2, v v’)
PS
- +
PA
 The Matrix representative is called (n), where n is the
- + dimention of the matrix
- +
 The character of the representation matrix is the sum of
diagonal elements.
PB

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Top view
Side view
S
O S O O S O
S
O O

O O A S B A S B

p(S) p(O)
c2 v

v’
(A+B) (A-B)
p(S) p(O) B S A
S
B S A

A S B

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Reduce- and Inreducible Representation

 Inspection of the representatives reveals that they are  According to the matrix representation, pA and pB are
all of block-diagonal form. mixed together.
 This shows that the ps is never mixed with the rest.  Using the LC, we can write the new basis as p1=pA+pB
and p2=pA-pB
- + + -
+
 The 3-D representative matrix ((3)) can be separated - - +

into (1)+ (2))

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Character Table
 The characters of all representations are tabulated in a
A S B
character table.
C2v E C2 v v’ h=4
A1 1 1 1 1 Z z2,y2,x2
A S B A S B A S B

A2 1 1 -1 -1 xy
B1 1 -1 1 -1 X xz
B2 1 -1 -1 1 y yx
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The Structure of Character Tables The Classification of LC of Orbitals

Group Symmetry Operations
Class
Order
(# operations)  NH3 sA

• LCAO:
C3v E 2C3 3v h=6 sB sC

A1 1 1 1 Z z2 , x 2 + y 2 this orbital is of symmetry species A1 and it contributes to

A2 1 1 -1 a1 MO in NH3.
E 2 -1 0 (x,y) (xy, x2-y2),(xz,yz)
# of degerneracy of each representative is specified
 NO2
Irreducible Symmetry by the symmetry property of E operation or (E). • LCAO:
Representations Properties ()
N
Labels A, B: 1-D E: 2-D T: 3-D O
A  (Cn) = 1 B  (Cn) = -1 O
1  (v) = 1 2  (v) = -1
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Orbitals with nonzero overalp Vanishing Integrals & Orbital Overlap

 Only orbitals of the same symmetry species may have  The value of integrals and orbital overlap is independent of
nonzero overlap, so only orbitalsof the same symmetry the orientation of the molecule.
species form bonding and antibonding combinations.
• I is invariant under any symmetry operation of the molecule,
otherwise it must be zero.
• For I not to be zero, the integrand f1f2 must have symmetry
species A1.
 Example: f1 = sB and f2 = sC of NH3
sB sC

not A1

 Problem: f1 = sN and f2 = sA +sB +sC of NH3

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Vanishing Integrals and Selectrion Rules

 Integrals of the form are common in quantum  In many cases, the product of functions f1 and f2 spans
mechanics. a sum of irreducible representations.
 For the integral to be nonzero, the product must span  In these cases, we have to decompose the reducible
A1 or contain a component that span A1. representation into irreducible representations
 The intensity of line spectra arises from a molecular transition
between some initial state i and a final state f and depends on
the electric transition dipole moment fi. C2v E C2 v v’
A2 1 1 -1 -1
C2v E C2 v v’
B1 1 -1 1 -1
B1 1 -1 1 -1 A2+B1 2 0 0 -2
z 1 1 1 1
A1 1 1 1 1
A1zB1 1 -1 1 1 if fzi does not
span species A1
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O-1s
SALC of H2O AO of H2O
HA-1s

a1
O-2s
HA-1s + HB-1s
b1
a1 a1 a1 b1 b2
O-2py
HA-1s HB-1s
b1 a1

C2V E C2 (z) σv σ’v b1 a1

A1 1 1 1 1 O-2pz z
A2 1 1 -1 -1 a1
B1 1 -1 1 -1
O-2px y
B2 1 -1 -1 1
b2 x
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MO of H2O
b1

b1
a1

a1 b1 b2

a1
b2

a1
a1

b1

a1
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Symmetry-adapted Linear Combinations Example of building SALC

 Symmetry-adapted linear combination (SALC) are the  s-orbitals of NH3
building blocks of LCAO-MO • Original basis are sN, sA, sB, sC
 To construct the SALC from basis: NH3
Original basis

1. Construct a table showing the effect of each operation sN sA sB sC

E sN sA sB sC
on each orbtial of the original basis. C3+ sN sB sC sA N C
2. To generate the combination of a specified symmetry C3- sN sC sA sB
species, take each column in turn and: v sN sA sC sB
A
B
a) Multiply each member of the column by the character of v’ sN sB sA sC
the corresponding operation. v “ sN sC sB sA For A1 combination (1,1,1,1,1,1)
b) Add together all the orbitals in each column with the
factors as determined in a).
c) Divide the sum by the order of the group.
37 when 38

References
1. Peter Atkin et. al, Physical Chemistry,
Oxford Univ press.
2. David O Hayward, Quantum Mechanics
for Chemists, RSC, 184 p.
3. Jack Barrett, Structure and Bonding,
RSC press, 178 p.

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