Systematic 

Reduction of Irreducible Representations
• For complex molecules with a large dimension reducible representation, identification of the
component irreducible representations and their quantitative contributions is not straight
forward.
• Fortunately, reducing such a representation for a group of finite order can be carried out
Fortunately
systematically using the following equation

ni : number of times the irreducible representation i occurs in the reducible representation

h : order of the group
c : class of operations
gc : number of operations in the class
i : character of the irreducible representation for the operations of the class
r : character of the reducible representation for the operations of the class

• The work of carrying out a systematic reduction is better organized by using the tabular
method, rather than writing out the individual equations for each irreducible representation
 Tabular Method
• To carry out the reduction, construct a work sheet with rows for each species, columns for each
product gc χi χr , a column for the sum of all gc χi χr products for each species  and a final
column for ni =  gc χi χr /h.
• Sample reducible representation worksheet for the Td point group given the reducible
representation r
• Products gc χi χr Td :

Character table for T
Character table for Td
(without last column for vector transformations and direct products)

Thus i = A2 + 2E + T2

• Checking our solution i = A2 + 2E + T2

d  =  1 + 2(2) + 3 = 8 = dr

• Does r compute ?
 Trouble Shooting
• The sum
s m across a row
ro is not divisible
di isible by
b the order h.
h
 An error has been made in one or more of the products, probably while changing signs
or multiplying from one row to the next; e.g.,

 An error was made in generating the original reducible representation; e.g.,

 You forgot to multiply by the number of operations in the class when generating the first
row; e.g.,
 Trouble Shooting (contd.)
• The sum
s m of the dimensions of the foundfo nd irreducible
irred cible representations does not equal
eq al the
dimension of the reducible representation.
 One or more of the lines for individual species is faulty in a way that happens to be divisible
by h; e.g.,

d  =  1 + 2(2) + 2(3) = 11 ≠ dr
 Reducing Representations with Imaginary Characters
• Certain groups (Cn , n ≥ 3; Cnh , n ≥ 3; S2n ; T ; Th ) have irreducible representations that contain
the imaginary integer i = (‐1)1/2 .
• Imaginary irreducible representations are always shown as complex conjugate pairs on
successive lines of the character table and are given a shared Mulliken symbol designation of a
doubly‐degenerate representation (e.g., E ).
• Both representations of a complex‐conjugate pair are individual non‐degenerate
representations in their own right.
• For real physical problems, if one imaginary representation is contained in the reducible
representation for a property, then the complex conjugate for that representation must also be
present in equal number.
• For convenience,
convenience complex conjugate pairs of representations are often added together to give a
real‐character representation, which is a reducible representation with dr = 2.
• We will always designate such combined real‐character representations with braces around the
Mulliken symbol of the complex conjugate pair; e.g., {E}.
• If a combined real‐character representation is used with the standard reduction formula, the
result given for the number of occurrences of the combined representataion (ni) will be twice
its true value.
• If using the standard reduction formula,
formula divide the result for any combined real
real‐character
character
representation of a complex‐conjugate pair by 2.
• For example, let us test the reducible representation in C4h r = 2Bg + {Eg} + Au

• Fi t we mustt generate
First t the
th complete
l t sett off characters
h t forf r according
di tot the
th C4h character
h t table
t bl

• Using the tabular method we then carry out a systematic reduction by generating a worksheet:

• Dividing the complex contribution by 2 we correctly obtain r = 2Bg + {Eg} + Au

 Group‐Subgroup Relationships
• When a structural change occurs, there is often a group‐subgroup relationship between the
original and new structures.
• If the new structure belongs to a point group that is a subgroup of the point group of the
original structure,
structure then descent in symmetry has occurred.
occurred
• Descent in symmetry may cause formerly degenerate properties to become distinct non‐
degenerate properties.
• If the new structure belongs
g to a higher‐order
g ggroup
p of which the old structure’s p
point ggroup
p is
a subgroup, then ascent in symmetry has occurred.
• Ascent in symmetry may cause formerly distinct non‐degenerate properties to become
degenerate.
• Observing
Ob i changes
h i degeneracy
in d (
(e.g., splitting
li i or coalescing
l i off bands
b d ini spectra)) can be
b
revealing of structure changes.
• Knowledge of group‐subgroup relationships can simplify the work of group theory applications
by solving the problem in a smaller‐order subgroup and correlating the results to the true
group.
 Oh Subgroups

• Groups that have a group‐subgroup A

relationship have related A A
M Oh (h = 48)
representations
p whose characters are A A
the same for the shared operations in A
the two groups. B
A A
M D 4h (h = 16)
A A
B

B
A A
M C 4v (h = 48)
A A
C

A C
A B A B
M C 3v (h = 6) M C 2v (h = 4)
A B A B
B C
 Group‐Subgroup Relationships
• Between a group and any of its subgroups, representations arising from the same vector basis
will have the same χ(r) values for all operations that occur in both groups.

Characters for shared operations in D4h and C4v

 Correlation diagram for D4h and C4v
• Those species in both groups that are not associated with a listed unit vector transformation
share a vector basis that is simply not one of those routinely listed.
 Lifting Degeneracies
• Degenerate representations may be spit into lower‐order representations (non‐degenerate or a
mixture of double and non‐degenerate representations) in a subgroup that is too small to have
higher‐order degeneracies.
Characters for shared operations in C4v and C2v
Characters for shared operations in C

• The characters of E in C4v form a reducible representation in C2v , E , which reduces to B1 + B2.
Correlation diagram for C4v and C2v
 Reducing Representations of Cv and Dh
• The standard reduction equation cannot be used with groups that have h = , like Cv and Dh.

Work‐around technique:
 Set up and
d solve
l the
h problem
bl in a finite
f subgroup
b
e.g., C2v for Cv , D2h for Dh .
 Correlate the results in the subgroup to the true infinite‐order group, using either a partial
correlation table or by matching shared vectors in the related groups.
 Complete correlations to an infinite group are not possible, because there are an infinite
number of irreducible representations.
 A partial correlation table is sufficient, because only a limited number of irreducible
representations in either Cv or Dh are related to real physical properties.
Partial correlation tables for Cv and Dh
 Direct Products of Irreducible Representations
• Any product of irreducible representations is also a representation of the group.

a b c = abc

• The character χ(R) for an operation R in a product representation is the product of the
characters of R in the component representations.
(R)a (R)b (R)c = abc(R)
• The dimension of a product representation, dp, is the product of the dimensions of the
component representations
 Relationships of Direct Products
1. If all the combined irreducible representations are non‐degenerate, then the product will be a
non‐degenerate representation, too.
e.g., a partial character table for C4v

The direct product B1 B2 results in the irreducible representation A2

 Relationships of Direct Products
2. The product of a non‐degenerate representation and a degenerate representation is a
degenerate representation.
e.g., a partial character table for C4v

The direct product B2 E results in the irreducible representation E

 Relationships of Direct Products
3. The direct product of any representation with the totally symmetric representation is the
representation itself.
e.g., a partial character table for C4v

The direct product A1 E results in the irreducible representation E

 Relationships of Direct Products
4. The direct product of degenerate representations is a reducible representation.
e.g., a partial character table for C4v

The direct product E E results in the reducible representation p

Systematic reduction gives p = A1 + A2 + B1 + B2

 Relationships of Direct Products
5. The direct product of an irreducible representation with itself is or contains the totally
symmetric representation.
e.g., a partial character table for C4v

The non‐degenerate self product B1 B1 results in the totally symmetric representation A1

The degenerate self product E E = p = A1 + A2 + B1 + B2

 Relationships of Direct Products
5. Only the direct product of a representation with itself is or contains the totally symmetric
representation. Moreover, the self‐product contains the totally symmetric representation only
once
Proof: How many times does the totally symmetric representation occur in any direct product?

where χi = χA = 1 for all R of the totally symmetric representation,

But p = a b for p = a b . Also, a and b must be orthogonal. Thus,

only the self‐product contains the totally symmetric representation, and then only once.
 Direct Products of Representations with Symmetry or 
Anti‐symmetry to a Specific Operation
Anti‐symmetry to a Specific Operation
In general:
sym × sym = sym
anti‐sym × anti‐sym = sym
anti‐sym × sym = anti‐sym
In terms of Mulliken symbols:

g × g = g
u × u = g
u × g = u
‘  × ‘  =  ‘
‘’  × ‘’  =  ‘
‘’  × ‘  =  ‘’