Lecture 1 Additional Material

Degenerate Representations
degenerate representations cannot be described by a single representation they necessarily have
two components
in non-degenerate representations (A and B symmetry labels), under a symmetry operation each
of the orbitals maps exactly (whithin a phase difference of 1) onto one of the others so that the
starting and finishing shapes are identical.
in a degenerate representation (E and T symmetry lables), the individual components do NOT
necessarily map onto each other, in this case the characters in the character table refer to the
transformation of both components!
in this document we will illustrate how the px and py are components form a degenerate
representation (E for the C3v point group), we will also examine how these orbitals behave
under the symmetry operations of the C3v point group

C3v E 2C3 3 v

A1 1 1 1 Tz
A2 1 1 -1
E 2 -1 0 (Tx, Ty)
C3v character table
y
start by taking a point on the tip of the orbitals under
1 consideration and determining it's position in terms of
0
x
the x and y axes, ie it's coordinates (x,y) or in our case
x
E y we will use the vector notation:
0 y
1
x x 1
the px orbital "point" has coordinates =
y 0
x 0
the py orbital "point" has coordinates =
y y 1
x one way to think of this is as a set of unit vectors
px py if the two vectors are positioned side by side a 2 by 2
y matrix is generated formed
1 0 = 1 0
x
0 1 0 1
unit vectors consider the transformation of each orbital (unit vector)
under E
o px and py remain the same
y o the equation for this (E operating on the points) is
1
0 given below:
x
1 0 1 0
E
0 1
y
E
0 0 1
1
x o the character is the sum of the diagonal terms of
the matrix which is just 1+1=2
o hence the character for E is 2
transformation under E o check this against your character table!

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 Lecture 1 Additional Material
y
1
1 consider the transformation under v
0 0
x o the equation for this is given below:
v
1 0 1 0
v y
v
0
0 1 0 1
1
x
v o the character is the sum of the diagonal terms of the
0 matrix which is just 1+(-1)=0
1
o hence the character for v is 0
transformation under v o check this against your character table for C3v

y consider the transformation under C3

C3 1
0 o the px and py orbitals are rotated 120
x
o the start point and finish points for the px diagram
are shown in more detail on the next page
C31 y o simple trigonometry is required to determine the x
0 and y coordinates for the final point
1
x o the key trigonometric identities are:

adjacent opposite
transformation under C3 cos = sin =
hypotenuse hypotenuse

2 30
hypotenuse 3
adjacent
60
opposite and 1

o consider the px point, the triangle generated by the

y start point rotation is shown to the left
o a more detailed representation is also given below:
x

y
= 120 y
x
x
end point = 30
start and finish points for rotation of the px y = cos 30
orbital "point"
end point x = sin 30
triangle used to generate the coordinates

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 Lecture 1 Additional Material
o we find that the coordinates for the final point are:
y
C3 1 sin 30
0 cos 30
x
o if the procedure is repeated for the py orbital we
sin 30
cos 30 cos 30
find that the coordinates are:
0
C31 y
sin 30
1 o but from the simple triangle shown earlier we know
x
1 3
that sin 30 = and cos 30 =
2 2
cos 30 o the equation for the C3 is given below:
sin 30
1 3

1 0 sin 30 cos 30 2 2
o C3 =
0 1 cos 30 sin 30 3 1

2 2

o the character is the sum of the diagonal terms of

1 1
C3v E 2C3 3 v this final matrix which is just + ( ) = 1
2 2
A1 1 1 1 Tz o hence the character for C3 is -1
A2 1 1 -1 o check this against your character table!

E 2 -1 0 (Tx, Ty)
thus we now know where the characters for the E
irreducible representation in C3v originate from
so far we have just used degenerate orbitals, but where do they come from?
o any two (or more!) wavefunctions that have the same energy are degenerate
o this just means that the H=E for =1 or =2 gives the same energy
o wavefunctions can be accidentally degenerate or degenerate by symmetry
put another way: wavefunctions that are related by a symmetry operation are degenerate
the equations below tell us than any (normalised) wavefunction composed of a linear
combination of degenerate functions also has the same energy
o sometimes we say that degenerate functions can rotate among themselves this just means
that the values of Ci can change without changing the energy of the linear combination
H i = Ei i i Ei = E
= c1 1 + c2 2 +!= ci i
i

H = H ci i = ci H i = ci E i = E ci i = E
! i i i i

we normally choose our degenerate wavefunctions to be orthogonal (ie they do not overlap!)