Lecture 2 Model Answers

In-Class Problems / Self-study Problems / Test Preparation: Lecture 2

• In-Class P1 C42 is equivalent to another
operation (in addition to C'2(x)), which one is
it?

o The Cl could also be reflected in the sv(xz)

plane Figure 1 [PtCl4]2¯ symmetry elements

• In-Class P2 What operation is S32 equivalent to? Draw a diagram proving the equality.
o S32 =C32
o in the figure below make sure you always rotate in the same direction, here the Sn was
rotated anticlockwise, so the Cn must also be rotated anticlockwise

F S32 F
C3(z) S31 B F B F
F F

F
B F identical
F final states S32=C32
σh(xy) 1
C3
F C 32 F
B F B F
F F

Figure 2 improper rotation

• In-Class P3 Use a representation table to determine the symmetry label for MO2.
E E C2 σv(xz) σv'(yz)
Γ 1

C2

C2 E C2 σv(xz) σv'(yz)
Γ 1 -1

σv(xz)
σv E C2 σv(xz) σv'(yz)
Γ 1 -1 1

σv(yz)
E C2 σv(xz) σv'(yz)
σv
Γ 1 -1 1 -1

Figure 3 Filling out the representation table for MO2

o matching the representation table against the C2v point group table we see that MO2 has b1
symmetry (note the small letter!)
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 Lecture 2 Model Answers
• In-Class P4 Draw a Lewis bonding diagram for IF5 and identify the molecular shape of IF5
using VSEPR theory. Determine the point group and draw all of the symmetry elements on a
diagram of the molecule. Identify if multiple operations in the character table are due to
multiple operations on the same element or multiple elements. For the highest rotation axis
identify, for any operations that are not-unique, the equivalent operation.
o each F contributes 7ve 6 of these will be in lone pairs, and 1e will contribute to a covalent
bond with I. The I has 7ve, 5 of these will contribute to covalent bonds with the F atoms, 2
will remain non-bonding as a lone pair.
F
F F square based pyramid
I
F F
y

x
z z
C4(z), C2(z)
x
F
y F F
F F
I C2'(x)
I
σda(xz)
F F F F
σvb
σva
σdb(yz)
C2b" C2a"
C2b'(y)

also one F coming out of the page

(removed for clarity)
Figure 4 identifying the symmetry operations of IF5

o point group
linear?NO
Td or Oh? NO
principle axis? YES C4
4C2 perpendicular to C4? NO
σh? NO
4σv? YES
therefor C4v
o there are 4 possible C4 operations, C41 and C43 are unique, C42 is the same as C21 and C44 is the
same as E. The 2C4 operations occur around the same element, the C4 axis
o the 2sd and 2sv operations are due to the presence of different symmetry elements (mirror
planes)

• Q1 Draw a diagram showing all the rotation operations for the C5 group on the cyclopentadienyl
anion

y
x
z C51 C52 C53 C54 C55
C5(z)

Figure 5 C5 rotation operations

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 Lecture 2 Model Answers

• Q2 Work out all of the S3n operations up to S36 for D3h z C3(z)
[H3]+ and determine the two unique S3 operations. y
o although we are using H which has no pAOs, we use a x H
pAO (as a tool) to ensure we take into account the H H
σh(xy)
correct symmetry.
o the unique operations are S31 and S35 Figure 6 D3h H3+

C3

S 31 S 32

σh
S36=E S32=C32
unique
S 36 S 33

S 35 S 34

σh
S34=C31 S33=σh
unique

Figure 7 identifying the unique S3 operations

• Q3 Which operation is S34 equivalent to? Draw a diagram clearly proving this equality.

S 32 S 33 S 34
z C3(z)
S3 1
y
x
H

H H identical
σh(xy) final states
C31
S34=C31

Figure 8 proof that the S34 operation is equivalent to the C31 operation

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 Lecture 2 Model Answers
• Q4 determine the symmetry label for the molecular orbitals shown for BH3
o for each example
1. draw a "representation table" for the MO
2. determine how the MO transforms under each symmetry operation
3. compare the representation to the irreducible representations on the character table
o (a) has a1' symmetry
o (b) has a2" symmetry (working shown below) Figure 9

x
z
y (a) (b)

D3h E 2C3 3C2 σh 2S3 3σv

σh(xy)
E σh

σh(xy)
C3 S3

C3(z) C3(z)
σv(yz)
C2 σv

C2(y)

D3h E 2C3 3C2 σh 2S3 3σv

Γ 1 1 -1 -1 -1 1

Figure 9 determining the symmetry label for MO (b)

• Q5 construct a representation table for the "z-axis" and determine which irreducible
representation it transforms as.
o The z-axis has the same phase properties as the pz AO of boron and MO(b) above (which
is just the pz AO of boron, AOs can also be MOs!). Thus we need never actually work
out the symmetry labels of the px, py or pz atomic orbitals because they will always have
the same symmetry labels as the x, y and z axes. The representation table is therefor the
same as that for the pz orbital and the symmetry label is a2".
• Q6 In your own words, using bullet points, write out the general procedure to determine the
symmetry label of a molecular orbital (abstraction from the Kolb cycle!)
o This is my process however you should go through the notes and an example and write out
the process for yourself in your own words!
1. determine the point group of the molecule
2. define the axis system
3. draw a representation table for the MO
4. determine how the MO transforms under each symmetry operation
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 Lecture 2 Model Answers
5. enter +1 for no phase change, -1 for a phase change
6. compare this representation to the irreducible representations from the character table
7. use a small letter for the symmetry label of a MO
• Q7 In your own words, using bullet points, write out the general procedure to determine the
character of a degenerate set of orbitals? (abstraction from the Kolb cycle!)
o This is my process however you should go through the notes and an example and write out
the process for yourself in your own words!
1. take point on tip of each orbital
2. form the starting matrix
3. perform the symmetry operation on the orbitals
4. write coordinates of each point
5. form the final matrix by combing the coordinates
6. the character is the TRACE of the final matrix
• Q8 The Tetrahedral Point Group (challenging but important!)
o discuss and illustrate the symmetry operations of the Td point group.
o hint: there are three useful ways of thinking
about a tetrahedral molecule, Figure 10, H
H
each one emphasises a different aspect of H
A A
symmetry: H H
H
(a) the C2 axes H H
(b) the C3 axes Figure 10 different ways to represent a Td molecule
(c) the cubic structure
o the "cube" may be less familiar to you, think of the H Td E 8C3 3C2 6S4 6σd h=24
atoms occupying opposite corners of a cube and the
A1 1 1 1 1 1
central atom A is at the center of the cube
o The character table for the Td point group is shown to A2 1 1 1 -1 -1
the left, Figure 11 and it tells us the key symmetry E 2 -1 2 0 0
operations in this group are E, 8C3 3C2 , 6S4 and 6σ d T1 3 0 -1 1 -1
• there are 8C3 operations T2 3 0 -1 -1 1 (TxTy Tz)

o a C3 axis lies along each bond, one C3 axis is shown in Figure 11 Td character table
Figure 12, the others are easily predicted because the
four H atoms are symmetry equivalent, if one H atom
has a C3 axis passing through it then they all will, hence C3
C3
there are four C3 axis symmetry elements H
o around each axis there are 3 possible C3 operations:
C31 C32 C33 , the last operation C33 = E is equivalent to the A
H
H
identity and so is already counted, there are then two H

symmetry operations associated with each C3 axis

o thus there are eight distinct C3 operations in Td : 8C3 H
C2
• there are 3C2 operations A
H
H
o a C2 axis lies between each pair of A-H bonds, Figure H

12, bisecting each pair of atoms and through the center

of each pair of faces in the cube, as there are 3 pairs of Figure 12 Td rotation operations
faces to each cube, there will be 3C2 axes
o as we associate only one operation with each C2 axis there are 3 C2 operations in Td

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 Lecture 2 Model Answers
• there are 6sd operations σd
looking from the side
looking from above

o a s mirror plane passes through each pair of H

atoms and contains a C2 axis, ie two mirror A
H
H
planes cross each pair of faces, Figure 13, H

these are dihedral mirror planes sd. Figure 13 Td sd mirror plane

o as there are 3 pairs of faces each with two
mirror planes there are 6sd operations in Td
• there are 6S4 operations
o each C2 axis has a coincident S4 axis, consider a rotation of 90º around this axis and then
reflection in a plane perpendicular to the axis through the center of the molecule. An example
of these elements for the S41 operation is given in Figure 14Error! Reference source not
found..
o notice that I am rotating counter clockwise, I can rotate in any direction I like as long as I am
consistent for all operations. If I call counter-clockwise the positive direction, then rotating in
the opposite direction becomes the "reverse" operation of C4-1.
o notice that after the C41 operation the "atom" is now "off" the molecule! However, once the
whole S41 operation is completed it is back "on" the molecule. This is a consequence of
neither the C4 nor the sh existing within the Td point group as separate elements!!
C4

σh
C41 σ h1

C4
S42=C21

C41 σ h1
C2

C21
Figure 14 top is the S41 operation, followed by the S42 operation on the bottom

o S42 (Figure) is the same as C21 operation and C2 lies to the left of S4 in the character table and
so this operation is not counted with the S4 operations. In addition the S44 operation is the
same as E and so is not counted either
o thus there are 2S4 operations per C2 axis, and as there are 3C2 axes there must be 6S4
operations in Td
• Thus we have shown that there are E, 8C3 3C2 , 6S4 and 6σ d operations for the Td point group.