412 10 Molecular symmetry
FOCUS 10 Molecular symmetry
TOPIC 10A Shape and symmetry
Discussion questions
D10A.1 Explain how a molecule is assigned to a point group.
D10A.2 List the symmetry operations and the corresponding symmetry
elements that occur in point groups.
Exercises
E10A.1(a) The CH3Cl molecule belongs to the point group C3v. List the
symmetry elements of the group and locate them in a drawing of the
molecule.
E10A.1(b) The BF3 molecule belongs to the point group D3h. List the symmetry
elements of the group and locate them in a drawing of the molecule.
E10A.2(a) Identify the group to which the naphthalene molecule belongs and
locate the symmetry elements in a drawing of the molecule.
E10A.2(b) Identify the group to which the trans-difluoroethene molecule
belongs and locate the symmetry elements in a drawing of the molecule.
E10A.3(a) Identify the point groups to which the following objects belong:
(i) a sphere, (ii) an isosceles triangle, (iii) an equilateral triangle, (iv) an
unsharpened cylindrical pencil.
E10A.3(b) Identify the point groups to which the following objects belong:
(i) a sharpened cylindrical pencil, (ii) a box with a rectangular cross-section,
(iii) a coffee mug with a handle, (iv) a three-bladed propeller (assume the
sector-like blades are flat), (v) a three-bladed propeller (assume the blades are
twisted out of the plane, all by the same amount).
E10A.4(a) List the symmetry elements of the following molecules and
name the point groups to which they belong: (i) NO2, (ii) PF5, (iii) CHCl3,
(iv) 1,4-difluorobenzene.
E10A.4(b) List the symmetry elements of the following molecules and
name the point groups to which they belong: (i) furan (1), (ii) γ-pyran (2),
(iii) 1,2,5-trichlorobenzene.
O Explain your answer.
O
1 Furan 2 γ-Pyran
Problems
P10A.1 List the symmetry elements of the following molecules and name the
point groups to which they belong: (a) staggered CH3CH3, (b) chair and boat
cyclohexane, (c) B2H6, (d) [Co(en)3]3+, where en is 1,2-diaminoethane (ignore
its detailed structure), (e) crown-shaped S8. Which of these molecules can be
(i) polar, (ii) chiral?
P10A.2 Consider the series of molecules SF6, SF5Cl, SF4Cl2, SF3Cl3. Assign each
to the relevant point group and state whether or not the molecule is expected
to be polar. If isomers are possible for any of these molecules, consider all
possible structures.
P10A.3 (a) Identify the symmetry elements in ethene and in allene, and assign
each molecule to a point group. (b) Consider the biphenyl molecule, Ph–Ph,
in which different conformations are possible according to the value of the
dihedral angle between the planes of the two benzene rings: if this angle is 0°,
D10A.3 State and explain the symmetry criteria that allow a molecule to be
polar.
D10A.4 State the symmetry criterion that allows a molecule to be optically active.
E10A.5(a) Assign (i) cis-dichloroethene and (ii) trans-dichloroethene to point
groups.
E10A.5(b) Assign the following molecules to point groups: (i) HF, (ii) IF7
(pentagonal bipyramid), (iii) ClF3 (T-shaped), (iv) Fe2(CO)9 (3), (v) cubane,
C8H8, (vi) tetrafluorocubane, C8H4F4 (4).
H
CO
Fe
CO
F
3 4
E10A.6(a) Which of the following molecules may be polar? (i) pyridine,
(ii) nitroethane, (iii) gas-phase BeH2 (linear), (iv) B2H6.
E10A.6(b) Which of the following molecules may be polar? (i) CF3H, (ii) PCl5,
(iii) trans-difluoroethene, (iv) 1,2,4-trinitrobenzene.
E10A.7(a) Identify the point group to which each of the possible isomers of
dichloronaphthalene belong.
E10A.7(b) Identify the point group to which each of the possible isomers of
dichloroanthracene belong.
E10A.8(a) Can molecules belonging to the point groups D2h or C3h be chiral?
E10A.8(b) Can molecules belonging to the point groups Th or Td be chiral?
Explain your answer.
the molecule is planar, if it is 90°, the two rings are perpendicular to one another.
For each of the following dihedral angles, identify the symmetry elements
present and hence assign the point group: (i) 0°, (ii) 90°, (iii) 45°, (iv) 60°.
P10A.4 Find the point groups of all the possible geometrical isomers for the
complex MA2B2C2 in which there is ‘octahedral’ coordination around the
central atom M and where the ligands A, B, and C are treated as structureless
points. Which of the isomers are chiral?
−
P10A.5‡ In the square-planar complex anion [trans-Ag(CF3)2(CN)2] , the
Ag–CN groups are collinear. (a) Assume free rotation of the CF3 groups
(i.e. disregarding the AgCF and AgCN angles) and identify the point group
‡
These problems were provided by Charles Trapp and Carmen Giunta.

of this complex ion. (b) Now suppose the CF3 groups cannot rotate freely
(because the ion was in a solid, for example). Structure (5) shows a plane
which bisects the NC–Ag–CN axis and is perpendicular to it. Identify the
point group of the complex if each CF3 group has a CF bond in that plane (so
the CF3 groups do not point to either CN group preferentially) and the CF3
groups are (i) staggered, (ii) eclipsed.
CF3
Ag
CN
CN
CF3
5
TOPIC 10B Group theory
Discussion questions
D10B.1 Explain what is meant by a ‘group’.
D10B.2 Explain what is meant by (a) a representative and (b) a representation
in the context of group theory.
D10B.3 Explain the construction and content of a character table.
Exercises
E10B.1(a) Use as a basis the 2pz orbitals on each atom in BF3 to find the
representative of the operation σ h. Take z as perpendicular to the molecular plane.
E10B.1(b) Use as a basis the 2pz orbitals on each atom in BF3 to find the
representative of the operation C3. Take z as perpendicular to the molecular plane.
E10B.2(a) Use the matrix representatives of the operations σ h and C3 in a basis
of 2pz orbitals on each atom in BF3 to find the operation and its representative
resulting from σ hC3. Take z as perpendicular to the molecular plane.
E10B.2(b) Use the matrix representatives of the operations σ h and C3 in a basis
of 2pz orbitals on each atom in BF3 to find the operation and its representative
resulting from C3σ h. Take z as perpendicular to the molecular plane.
E10B.3(a) Show that all three C2 operations in the group D3h belong to the same
class.
E10B.3(b) Show that all three σ v operations in the group D3h belong to the same
class.
E10B.4(a) For the point group C2h, confirm that all the irreducible representations
are orthonormal according to the property defined in eqn 10B.7. The character
table will be found in the online resources.
Problems
P10B.1 The group C2h consists of the elements E, C2, σ h, i. Construct the group
multiplication table. Give an example of a molecule that belongs to the group.
P10B.2 The group D2h has a C2 axis perpendicular to the principal axis and a
horizontal mirror plane. Show that the group must therefore have a centre of
inversion.
P10B.3 Consider the H2O molecule, which belongs to the group C2v. Take the
molecule to lie in the yz-plane, with z directed along the C2 axis; the mirror
plane σ v′ is the yz-plane, and σ v is the xz-plane. Take as a basis the two H1s
orbitals and the four valence orbitals of the O atom and set up the 6 × 6
Exercises and problems 413
P10A.6‡ B.A. Bovenzi and G.A. Pearse, Jr. (J. Chem. Soc. Dalton Trans.,
2763 (1997)) synthesized coordination compounds of the tridentate ligand
pyridine-2,6-diamidoxime (C7H9N5O2, 6). Reaction with NiSO4 produced
a complex in which two of the essentially planar ligands are bonded at
right angles to a single Ni atom. Identify the point group and the symmetry
operations of the resulting [Ni(C7H9N5O2)2]2+ complex cation.
HO OH
N N
N
H2N NH2
6
D10B.4 Explain what is meant by the reduction of a representation to a direct
sum of irreducible representations.
D10B.5 Discuss the significance of the letters and subscripts used to denote the
symmetry species of an irreducible representation.
E10B.4(b) For the point group D3h, confirm that the irreducible representation
E′ is orthogonal (in the sense defined by eqn 10B.7) to the irreducible
representations A′1, A′2 , and E″.
E10B.5(a) By inspection of the character table for D3h, state the symmetry
species of the 3p and 3d orbitals located on the central Al atom in AlF3.
E10B.5(b) By inspection of the character table for D4h, state the symmetry
species of the 4s, 4p, and 3d orbitals located on the central Ni atom in Ni(CN)42−.
E10B.6(a) What is the maximum degeneracy of the wavefunctions of a particle
confined to the interior of an octahedral hole in a crystal?
E10B.6(b) What is the maximum degeneracy of the wavefunctions of a particle
confined to the interior of an icosahedral nanoparticle?
E10B.7(a) What is the maximum possible degree of degeneracy of the orbitals
in benzene?
E10B.7(b) What is the maximum possible degree of degeneracy of the orbitals
in 1,4-dichlorobenzene?
matrices that represent the group in this basis. (a) Confirm, by explicit matrix
multiplication, that C2σ v = σ v′ and σ vσ v′ = C2. (b) Show that the representation
is reducible and spans 3A1 + B1 + 2B2.
P10B.4 Find the representatives of the operations of the group Td in a basis of
four H1s orbitals, one at each apex of a regular tetrahedron (as in CH4). You
need give the representative for only one member of each class.
P10B.5 Find the representatives of the operations of the group D2h in a basis
of the four H1s orbitals of ethene. Take the molecule as lying in the xy-plane,
with x directed along the C–C bond.
414 10 Molecular symmetry

P10B.6 Confirm that the representatives constructed in Problem P10B.5 P10B.9 The algebraic forms of the f orbitals are a radial function multiplied by
reproduce the group multiplications C2zC y2 = C x2, σ xzC2z = C y2, and iC y2 = σ xz. one of the factors (a) z(5z2 − 3r2), (b) y(5y2 − 3r2), (c) x(5x2 − 3r2), (d) z(x2 − y2),
(e) y(x2 − z2), (f) x(z2 − y2), (g) xyz. Identify the irreducible representations
P10B.7 The (one-dimensional) matrices D(C3) = 1 and D(C2) = 1, and D(C3) = 1
spanned by these orbitals in the point group C2v. (Hint: Because r is the radius,
and D(C2) = −1 both represent the group multiplication C3C2 = C6 in the group
r 2 is invariant to any operation.)
C6v with D(C6) = +1 and −1, respectively. Use the character table to confirm
these remarks. What are the representatives of σ v and σ d in each case? P10B.10 Using the same approach as in Section 10B.3c find the representatives
using as a basis two wavefunctions ψ2,3 = (2/L)sin(2πx/L)sin(3πy/L) and ψ3,2 =
P10B.8 Construct the multiplication table of the Pauli spin matrices, σ, and the
(2/L)sin(3πx/L)sin(2πy/L) in the point group C4, and hence show that these
2 × 2 unit matrix:
functions span a degenerate irreducible representation.
⎛ 0 1 ⎞ ⎛ 0 −i ⎞ ⎛ 1 0 ⎞ ⎛ 1 0 ⎞
σ x =⎜ ⎟ σ y = ⎜ i 0 ⎟ σ z = ⎜ 0 −1 ⎟ σ 0 = ⎜ 0 1 ⎟
⎝ 1 0 ⎠ ⎝ ⎠ ⎝ ⎠ ⎝ ⎠
Do the four matrices form a group under multiplication?

TOPIC 10C Applications of symmetry

Discussion questions
D10C.1 Identify and list four applications of character tables. D10C.2 Explain how symmetry arguments are used to construct molecular
orbitals.

Exercises
E10C.1(a) Use symmetry properties to determine whether or not the integral E10C.6(b) The ClO2 molecule (which belongs to the group C2v) was trapped in
∫pxzpzdτ is necessarily zero in a molecule with symmetry C2v. a solid. Its ground state is known to be B1. Light polarized parallel to the y-axis
E10C.1(b) Use symmetry properties to determine whether or not the integral (parallel to the OO separation) excited the molecule to an upper state. What is
∫pxzpzdτ is necessarily zero in a molecule with symmetry D3h. the symmetry species of that state?
E10C.2(a) Is the transition A1 → A2 forbidden for electric dipole transitions in E10C.7(a) A set of basis functions is found to span a reducible representation
a C3v molecule? of the group C4v with characters 5,1,1,3,1 (in the order of operations in the
E10C.2(b) Is the transition A1g → E2u forbidden for electric dipole transitions in character table in the Resource section). What irreducible representations does
a D6h molecule? it span?
E10C.7(b) A set of basis functions is found to span a reducible representation
E10C.3(a) Show that the function xy has symmetry species B1g in the group D2h.
of the group D2 with characters 6,−2,0,0 (in the order of operations in the
E10C.3(b) Show that the function xyz has symmetry species Au in the group D2h.
character table in the Resource section). What irreducible representations does
E10C.4(a) Consider the C2v molecule OF2; take the molecule to lie in the it span?
yz-plane, with z directed along the C2 axis; the mirror plane σ v′ is the yz-plane,
E10C.8(a) A set of basis functions is found to span a reducible representation of
and σ v is the xz-plane. The combination pz(A) + pz(B) of the two F atoms
the group D4h with characters 4,0,0,2,0,0,0,4,2,0 (in the order of operations in
spans A1, and the combination pz(A) − pz(B) of the two F atoms spans B2.
the character table in the Resource section). What irreducible representations
Are there any valence orbitals of the central O atom that can have a non-zero
does it span?
overlap with these combinations of F orbitals? How would the situation be
E10C.8(b) A set of basis functions is found to span a reducible representation
different in SF2, where 3d orbitals might be available?
of the group Oh with characters 6,0,0,2,2,0,0,0,4,2 (in the order of
E10C.4(b) Consider the same situation as in Exercise E10C.4(a). Find the
operations in the character table in the Resource section). What irreducible
irreducible representations spanned by the combinations py(A) + py(B) and
representations does it span?
py(A) − py(B). Are there any valence orbitals of the central O atom that can
have a non-zero overlap with these combinations of F orbitals? E10C.9(a) What states of (i) benzene, (ii) naphthalene may be reached by
electric dipole transitions from their (totally symmetrical) ground states?
E10C.5(a) Consider the C2v molecule NO2. The combination px(A) − px(B) of
E10C.9(a) What states of (i) anthracene, (ii) coronene (7) may be reached by
the two O atoms (with x perpendicular to the plane) spans A2. Is there any
electric dipole transitions from their (totally symmetrical) ground states?
valence orbital of the central N atom that can have a non-zero overlap with
that combination of O orbitals? What would be the case in SO2, where 3d
orbitals might be available?
E10C.5(b) Consider BF3 (point group D3h). There are SALCs from the F valence
orbitals which transform as A″2 and E″. Are there any valence orbitals of the
central B atom that can have a non-zero overlap with these SALCs? How
would your conclusion differ for AlF3, where 3d orbitals might be available?
E10C.6(a) The ground state of NO2 is A1 in the group C2v. To what excited states
may it be excited by electric dipole transitions, and what polarization of light
is it necessary to use? 7 Coronene

Problems
P10C.1 What irreducible representations do the four H1s orbitals of CH4 span?
Are there s and p orbitals of the central C atom that may form molecular
orbitals with them? In SiH4, where 3d orbitals might be available, could
these orbitals play a role in forming molecular orbitals by overlapping with
the H1s orbitals?
P10C.2 Suppose that a methane molecule became distorted to (a) C3v
symmetry by the lengthening of one bond, (b) C2v symmetry, by a kind of
scissors action in which one bond angle opened and another closed slightly.
Would more d orbitals on the carbon become available for bonding?
2
P10C.3 Does the integral of the function 3x − 1 necessarily vanish when
integrated over a symmetrical range in (a) a cube, (b) a tetrahedron, (c) a
hexagonal prism, each centred on the origin?
P10C.4‡ In a spectroscopic study of C60, Negri et al. (J. Phys. Chem. 100,
10849 (1996)) assigned peaks in the fluorescence spectrum. The molecule
has icosahedral symmetry (Ih). The ground electronic state is A1g, and the
lowest-lying excited states are T1g and Gg. (a) Are photon-induced transitions
allowed from the ground state to either of these excited states? Explain your
answer. (b) What if the molecule is distorted slightly so as to remove its centre
of inversion?
P10C.5 In the square planar XeF4 molecule, consider the symmetry-adapted
linear combination p1= pA − pB + pC − pD, where pA, pB, pC, and pD are 2pz
atomic orbitals on the fluorine atoms (clockwise labelling of the F atoms).
Decide which of the various s, p, and d atomic orbitals on the central Xe atom
can form molecular orbitals with p1.
P10C.6 The chlorophylls that participate in photosynthesis and the haem
(heme) groups of cytochromes are derived from the porphine dianion group
Exercises and problems 415
(8), which belongs to the D4h point group. The ground electronic state is A1g
and the lowest-lying excited state is Eu. Is a photon-induced transition allowed
from the ground state to the excited state? Explain your answer.
N
N– N–
N
8
P10C.7 Consider the ethene molecule (point group D2h), and take it as lying in
the xy-plane, with x directed along the C–C bond. By applying the projection
formula to one of the hydrogen 1s orbitals generate SALCs which have
symmetry Ag, B2u, B3u, and B1g. What happens when you try to project out a
SALC with symmetry B1u?
P10C.8 Consider the molecule F2C=CF2 (point group D2h), and take it as lying
in the xy-plane, with x directed along the C–C bond. (a) Consider a basis
formed from the four 2pz orbitals from the fluorine atoms: show that the basis
spans B1u, B2g, B3g, and Au. (b) By applying the projection formula to one of the
2pz orbitals, generate the SALCs with the indicated symmetries. (c) Repeat the
process for a basis formed from four 2px orbitals (the symmetry species will
be different from those for 2pz).