COLLEGE OF NATURAL AND COMPUTATIONAL SCIENCES

SCHOOL OF POST GRADUATE STUDIES

DEPARTMENT OF CHEMISTRY

COURSE TITLE: ADVANCED INORGANIC CHEMISTRY

ASSIGNMENT OF ADVANCED INORGANIC CHEMISTRY

BY
ADNEW WOELEBO
ID NO: PRPGNCS/001/17

SUBMITTED TO: DR. BELETE YILMA (Associate professor)

January 2025 G.C

ARBA MINCH, ETHIOPIA
 ASSIGNMENT: ONE
1. Determine the point groups of the following molecules and ions:
Answer:

(a) XeF4

XeF4 is not linear. Its highest order rotation axis is C 4. It has four C2 axes
perpendicular to the C4 axis and is therefore in the D set of groups. It has a horizontal
plane perpendicular to the C4 axis. Its point group is D4h.

(b) ) SF4

SF4 is not linear. Its highest order (and only) rotation axis is a C2 axis passing
through the lone pair. The molecule has no other C 2 axes. It has no mirror plane
perpendicular to the principal C2 axis. It has no horizontal mirror plane. It has two
vertical mirror planes containing the C2 axis. The point group is C2v.

(c) IOF3

 The molecule has only a mirror plane. Its point group is Cs.

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 (c) Ethane (staggered conformation)

 Staggered ethane has three mirror planes, each containing the C–C bond axis and passing
through two hydrogens on opposite ends of the molecule. It has a C3 axis collinear with
the carbon–carbon bond and three C2 axes bisecting the angles between the mirror
planes. Staggered ethane also has a center of inversion and an S6 axis collinear with the
C3 axis. Ethane in the staggered conformation has 2 C3 axes (the C–C line),
3 perpendicular C2 axes bisecting the C–C line, in the plane of the two C’s and the H’s
on opposite sides of the two C’s. No h, 3d, i, S6. D3d. Its point group is D3d.

(e) Ethane (eclipsed conformation)

 Ethane in eclipsed conformation has two C3 axes (the C–C line), three
perpendicular C2 axes bisecting the C–C line, in the plane of the two C’s and the
H’s on the same side of the two C’s. Mirror planes include h and 3d. Its point
group is D3h.
(f) Chloroethane (staggered conformation)
Chloroethane in the staggered conformation has only one mirror plane, through
both C’s, the Cl, and the opposite H on the other C. Its point group is Cs.

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 (g) 1, 2-Dichloroetliane (staggered anti conformation.)
 1,2-dichloroethane in the trans conformation has a C2 axis perpendicular to the
C–C bond and perpendicular to the plane of both Cl’s and both C’s, a h plane
through both Cl’s and both C’s, and an inversion center. Its point group is C2h.
2. determine the point group for :
(a) A sheet of typing paper
 A sheet of typing paper has three perpendicular C2 axes and three perpendicular
mirror planes. Its point group is D2h.
(b) An Erlenmeyer flask (no label)
 An Erlenmeyer flask has an infinite-fold rotation axis and an infinite number of
v planes, Its point group is Cv.
(c) A screw
 A screw has no symmetry operations other than the identity, for a C1
classification. Its point group is C1
(d) The number 96
 The number 96 (with the correct type font) has a C2 axis perpendicular to the
plane of the paper, making it. Its point group is C2h.
(e) Five examples of objects from everyday life; select items from five different
1. A coffee mug; Symmetry element c2 axis through handle, one vertical mirror.
Its point group c2v
2. A soccer ball; Symmetry elements C60 axis. Multiple σv and σd planes. Point
groups Oh
3. A table; the symmetry elements are C4axis through the center and horizontal
mirror plane and has vertical mirror plane. Point group is D4h
4. A bicycle wheel; the symmetry elements are cn axis through the center and
multiple σv planes. The point group is D∞h
5. A pair of scissors; the symmetry elements are C2 axis through the pivot point
and it has one vertical mirror plane. The point group is C2v
(f) A pair of eyeglasses (assuming lenses of equal strength)
 A pair of eyeglasses has only a vertical mirror plane. Its point group is Cs.

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3. Reduce the following representations to their irreducible representations in the point group
Indicated
a.
C2h E C2 I σh
Г 4 0 2 2
Solution
1
nAg= (1) (4) (1) + (1) (0) (1) + (1) (2) (1) + (1) (2) (1) = 2
4
1
nBg = (1) (4) (1) + (1) (0) (-1) + (1) (2) (1) + (1) (2) (-1) = 1
4
1
nAu = (1) (4) (1) + (1) (0) (1) + (1) (2) (-1) + (1) (2) (-1) = 0
4
1
nBu = (1) (4) (1) + (1) (0) (-1) + (1) (2) (-1) + (1) (2) (1) = 1
4
Therefore, Г = 2Ag + Bg + Bu
b.
Td E 8C3 3C2 6S4 6σd
Г 4 1 0 0 2
Solution
Character table for Td
Td E 8C3 3C2 6S4 6σd
A1 1 1 1 1 1
A2 1 1 1 -1 -1
E 2 -1 2 0 0
T1 3 0 -1 1 -1
T2 3 0 -1 -1 1
Г 4 1 0 0 2

1
A1 = (1) (4) (1) + (8) (1) (1) + (3) (0) (1) + (6) (0) (1) + (6) (2) (1) = 1
24
1
A2 = (1) (4) (1) + (8) (1) (1) + (3) (0) (1) + (6) (0) (-1) + (6) (2) (-1) = 0
24
1
E = (1) (4) (2) + (8) (1) (-1) + (3) (0) (2) + (6) (0) (0) + (6) (2) (0) = 0
24
1
T1 = (1) (4) (3) + (8) (1) (0) + (3) (0) (-1) + (6) (0) (1) + (6) (2) (-1) = 0
24

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 1
T2 = (1) (4) (3) + (8) (1) (0) + (3) (0) (-1) + (6) (0) (-1) + (6) (2) (1) = 1
24
Adding the characters of A1 and T2 for each operation confirms the result
Therefore, Г = A1+ T2

c.
C4v E 2C4 C2 2σv 2σd
Г 7 -1 -1 -1 -1
Solution
Character table for C4v
C4V E 2C4 C2 2σv 2σd
A1 1 1 1 1 1
A2 1 1 1 -1 -1
B1 1 -1 1 1 -1
B2 1 -1 1 -1 1
E 2 0 -2 0 0
Г3 7 -1 -1 -1 -1
Solution

1
A1= (1) (7) (1) + (2) (-1) (1) + (-1) (1) (1) + (2) (-1) (1) + (2) (-1) (1) = 0
8
1
A2 = (1) (7) (1) + (2) (-1) (1) + (-1) (1) (1) + (2) (-1) (-1) + (2) (-1) (-1) = 1
8
1
B1 = (1) (7) (1) + (2) (-1) (-1) + (-1) (1) (1) + (2) (-1) (1) + (2) (-1) (-1) = 1
8
1
B2 = (1) (7) (1) + (2) (-1) (-1) + (-1) (1) (1) + (2) (-1) (-1) + (2) (-1) (1) = 1
8
1
E= ¿ 1) (7 (2) + (2) -1) (0) + (-1) (1) (-2) + (2) (-1) (0) + (2) (-1) (0) = 2
8
Therefore, Г3 = A2 + B1+ B2 + 2E
4. Analysis of the x, y, and z coordinates of each atom in NH3 gives the following
representation.
C3v E 2C3 3σv

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 Г 12 0 2

Character table for C3v

C3v E 2C3 3σv
A1 1 1 1 z
A2 1 1 -1
E 2 -1 0 Rz
Г 12 0 2 (x, y) Rx, Ry
a. Reduce r to its irreducible representations.
Solution
1
A1= (12) (1) (1) + (2) (0) (1) + (3) (2) (1) = 3
6
1
A2 = ((12) (1) (1) + (2) (0) (1) + (3) (2) (-1) = 1
6
1
E= ¿ 12) (1 (2) + (2) (0) (-1) + (3) (2) (0) = 4
6
Therefore, Г =3 A1 +A2 + 4E
b. Classify the irreducible representations into translational, rotational, and vibrational modes
Solution
 Translational: based on the x, y, and z entries in the table.
Translational: A1 +E
 Rotational: based on the Rx, Ry, and Rz entries in the table.
Rotational: A2 + E
 Vibrational: 2A1 + 2E remaining from total: the A1 Vibrational are symmetric stretch
and symmetric bend. The E Vibrations are symmetric
Vibrational mode: 2A1 + 2E

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c. Show that the total number of degrees of freedom = 3N.
 There are three Translational mode, three Rotational mode, and Six Vibrational modes
for a total of 12. With 4 atom in the molecule, 3N = 12, so there are 3N degrees of
freedom in the ammonia molecule.
d. Which vibrational modes are infrared
 All the vibrational modes are IR active (all have x, y, or z symmetry).

5. Ethylene is a molecule of D2h symmetry.

a. List all the symmetry operations of ethylene.
b. Write a transformation matrix for each symmetry operation that describes the effect of
that operation on the coordinates of a point x, y, z.
c. Using the characters of your transformation matrices, obtain a reducible representation.
d. Using the diagonal elements of your matrices, obtain three of the D2h irreducible
representations.
e. Show that your irreducible representations are mutually orthogonal
Solution
a. D2h molecules have E, C2(z), C2(y), C2(x), i, σ(xy), σ(xz) and σ(yz)

[ ] [ ]
1 0 0 −1 0 0
E: 0 1 0 C2(y): 0 1 0
0 0 1 0 0 −1

[ ] [ ]
−1 0 0 1 0 0
C2(z): 0 −1 0 C2(x): 0 −1 0
0 0 1 0 0 −1

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 [ ] [ ]
−1 0 0 1 0 0
i: 0 −1 0 σ(xz): 0 −1 0
0 0 −1 0 0 1

[ ] [ ]
1 0 0 −1 0 0
σ(xy): 0 1 0 σ(yz): 0 1 0
0 0 −1 0 0 1

b. & d. Character table of D2h

D2h E C2(z) C2(y) C2(x) I σ(xy) σ(xz) σ(yz)

𝒳 3 -1 -1 -1 -3 1 1 1
Г1 1 -1 -1 1 -1 1 1 -1 Matching B3u
Г2 1 -1 1 -1 -1 1 -1 1 Matching B2u
Г3 1 1 -1 -1 -1 -1 1 1 Matching B1u
e. The irreducible representations are mutually orthogonal.
Г1 x Г2 = 1 × 1 + (–1) × (–1) + (–1) × 1 + 1 × (–1) + (–1) × (–1) + 1 × 1 + 1 × (–1) + (–1)
×1=0
Г1 x Г3 = 1 × 1 + (–1) × 1 + (–1) × (–1) + 1 × (–1) + (–1) × (–1) + 1 × (–1) + 1 × 1 + (–1)
×1=0
Г2 x Г3 = 1 × 1 + (–1) × 1 + 1 × (–1) + (–1) × (–1) + (–1) × (–1) + 1 × (–1) + (–1) × 1 + 1
×1=0
6. Using the D2d character table:
a. Determine the order of the group.
b. Verify that the E irreducible representation is orthogonal to each of the other
irreducible representations.
c. For each of the irreducible representations, verify that the sum of the squares of the
characters equals the order of the group.
d. Reduce the following representations to their component irreducible representations
Solution

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 a. h = 8 (the total number of symmetry operations)
b. A1 × E = 1 × 2 + 2 × 1 × 0 +1 × (–2) + 2 × 1 × 0 + 2 × 1 × 0 = 0
A2 × E = 1 × 2 + 2 × 1 × 0 +1 × (–2) + 2 × (–1) × 0 + 2 × (–1) × 0 = 0
B1 × E = 1 × 2 + 2 × (–1) × 0 +1 × (–2) + 2 × 1 × 0 + 2 × (–1) × 0 = 0
B2 × E = 1 × 2 + 2 × (–1) × 0 +1 × (–2) + 2 × (–1) × 0 + 2 × 1 × 0 = 0
c. E: 4 + 2 × 0 + 4 + 2 × 0 + 2 × 0 = 8
A1: 1 + 2 × 1 + 1 + 2 × 1 + 2 × 1 = 8
A2: 1 + 2 × 1 + 1 + 2 × 1 + 2 × 1 = 8
B1: 1 + 2 × 1 + 1 + 2 × 1 + 2 × 1 = 8
B2: 1 + 2 × 1 + 1 + 2 × 1 + 2 × 1 = 8

d. Г1 = 2A1 + B1 + B2 + E:
A1: 1/8[1 × 6 + 2 × 1 × 0 + 1 × 2 + 2 × 1 × 2 + 2 × 1 × 2] = 2
A2: 1/8[1 × 6 + 2 × 1 × 0 + 1 × 2 + 2 × (–1) × 2 + 2 × (–1) × 2] = 0
B1: 1/8[1 × 6 + 2 × (–1) × 0 + 1 × 2 + 2 × 1 × 2 + 2 × (–1) × 2] = 1
B2: 1/8[1 × 6 + 2 × (–1) × 0 + 1 × 2 + 2 × (–1) × 2 + 2 × 1 × 2] = 1
E: 1/8[2 × 6 + 2 × 0 × 0 + (–2) × 2 + 2 × 0 × 2 + 2 × 0 × 2] = 1
Г2 = 3 A1 + 2A2 + B1:
A1: 1/8[1 × 6 + 2 × 1 × 4 + 1 × 6 + 2 × 1 × 2 + 2 × 1 × 0] = 3
A2: 1/8[1 × 6 + 2 × 1 × 4 + 1 × 6 + 2 × (–1) × 2 + 2 × (–1) × 0] = 2

B1: 1/8[1 × 6 + 2 × (–1) × 4 + 1 × 6 + 2 × 1 × 2 + 2 × (–1) × 0] = 1

B2: 1/8[1 × 6 + 2 × (–1) × 4 + 1 × 6 + 2 × (–1) × 2 + 2 × 1 × 0] = 0

E: 1/8[2 × 6 + 2 × 0 × 4 + (–2) × 6 + 2 × 0 × 2 + 2 × 0 × 0] = 0
7. Using the x, y, and z coordinates for each atom in SF6, determine the reducible
representation, reduce it, classify the irreducible representations into translational,
rotational, and vibrational modes, and decide which vibrational modes are infrared active.
Solution

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  For SF6, the axes of the sulfur should point at three of the fluorines. The fluorine
axes can be chosen in any way, as long as one from each atom is directed toward the
sulfur atom.
 There are seven atoms with three axes each, for a total of 21.
Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd
Г 21 0 –1 3 –3 –3 –1 0 5 3
T1u 3 0 –1 1 –1 –3 –1 0 1 1 (x,y,z)
T1g 3 0 –1 1 –1 3 1 0 –1 –1 (Rx, Ry, Rz)
A1g 1 1 1 1 1 1 1 1 1 1
A2u 1 1 –1 –1 1 1 –1 1 1 –1
Eg 2 –1 0 0 2 2 0 –1 2 0 (2z2 – x2 – y2, x2 – y2)
T2u 3 0 1 –1 –1 –3 1 0 1 –1
T2g 3 0 1 –1 –1 3 –1 0 –1 1 (xy, xz, yz)

 Reduction of Г gives Г = 3T1u + T1g + A1g + Eg + T2g + T2u. T1u accounts for translation
and also infrared active vibrational modes. T1g is rotation. The remainder are infrared-
inactive vibrations.

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