1.3 Summary of Symmetry Operations, Symmetry Elements, and Point Groups.

Rotation axis. A rotation by 360˚/n that brings a three-dimensional body into an

^
equivalent configuration comprises a Cn symmetry operation. If this operation is performed a
^ ^ ^
second time, the product Cn Cn equals a rotation by 2(360˚/n), which may be written as Cn2. If n
^ ^
is even, n/2 is integral and the rotation reduces to Cn/2. In general, a Cnm operation is reduced
^ ^
by dividing m and n by their least common divisor (e.g., C96 = C32). Continued rotation by

360˚/n generates the set of operations:

^ ^ ^ ^ ^
Cn, Cn2, Cn3, Cn4, ... Cnn
^ ^ ^ ^
where Cnn = rotation by a full 360˚ = E the identity. Therefore Cnn+m = Cnm. Operations
resulting from a Cn symmetry axis comprise a group that is isomorphic to the cyclic group of
order n. If a molecule contains no other symmetry elements than Cn, this set constitutes the
symmetry point group for that molecule and the group specified is denoted Cn. When additional
symmetry elements are present, C n forms a proper subgroup of the complete symmetry point
group. Molecules that possess only a Cn symmetry element are rare, an example being
Co(NH2CH2CH2NH2)2Cl2+, which possesses a sole C2 symmetry element.

N
Cl N
Co

Cl N
N

^
One special type of Cn operation exists only for linear molecules (e.g., HCl). Rotation by

any angle around the internuclear axis defines a symmetry operation. This element is called
^
C• axis and an infinite number of operations C•f are associated with the element where f

denotes rotation in decimal degrees.

We already saw that molecules may contain more than one rotation axis. In BF3,

depicted below, a three-fold axis emerges from the plane of the paper intersecting the center of
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F F

F currentpoint 192837465
triangular projection. Three C2 axes containing each B-F bond lie in the plane of the molecule
perpendicular to the three-fold axis. The rotation axis of highest order (i.e., C3) is called the
principal axis of rotation. When the principal Cn axis has n even, then it contains a C2 operation
associated with this axis. Perpendicular C2 axes and their associated operations must be denoted

with prime and double prime superscripts.

Reflection planes. Mirror planes or planes of reflection are symmetry elements whose
associated operation, reflection in the plane, inverts the projection of an object normal to the
mirror plane. That is, reflection in the xy plane carries out the transformation (x,y,z) ∅ (x,y,-z).
Mirror planes are denoted by the symbol s and given the subscripts v, d, and h according to the

following prescription. Planes of reflection that are perpendicular to a principal rotation axis of
even or odd order are named sh (e.g., the plane containing the B and 3F atoms in BF3). Mirror
planes that contain a principal rotation axis are called vertical planes and designated sv. For

example, in BF3 there are three sv planes, each of which contains the boron atom, fluorine atom,
and is perpendicular to the molecular plane. Notice that for an odd n-fold axis there will be n sv
mirror planes which are similar. That is if we have one sv plane, then by operation of Cn a total
of n times, we generate n equivalent mirror planes. The n s v operations comprise a conjugate
class. For even n the sv planes fall into two classes of n/2 sv and n/2 sd planes, as illustrated

earlier in the chapter.

Rotoreflection axes or improper rotation axes. This new operation is best thought of as
the stepwise product of a rotation, and reflection in a plane perpendicular to the rotation axis.
^
We need to introduce it since a product such as C6 ^sh is not equal to either a normal rotation or

reflection. To satisfy group closure a new symmetry operation must be introduced. An

21
 22

^ ^
inversion operation is the simplest rotoreflection operation and is given the name S2 or i . That
S^2 = ^i is immediately apparent because ^i.(x,y,z) = (-x,-y,-z) and C2(z) ^s(xy).(x,y,z) =
^
^ ^ ^ ^
C2(z).(x,y,-z) = (-x,-y,-z). Because Cn and ^sh commute we have Sn = Cn ^sh for the general
^
rotoreflection operation. Since ^shn = E for even m and for m odd ^shm = ^sh, an Sn axis requires
simultaneous independent existence of a Cn/2 rotation axis and an inversion center when n is

even. For example, an S6 axis generates the operations for the point group S6. They are shown

below.
S^6, S^62 = C32 ^sh2 = C32, S^63 = S^2 = C2 ^sh = î, S^64 = C32, S^65 = C65 ^sh, S^66 = E
^ ^ ^ ^ ^ ^
.
An odd order rotoreflection axis requires independent existence of a Cn axis and a sh symmetry
element. An S7 axis generates the following operations.
S^7, S^72 = C72, S^73, S^74 = C74, S^75, S^76 = C76, S^77 = C77 ^sh7 = ^sh, S^78 = C78 =
^ ^ ^ ^ ^
^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^
C7, S79 = C72 ^sh, S710 = C73, S711 = C74 ^sh, S712 = C75, S713 = C76 ^sh, S714 = E
The S7 axis generates a cyclic group of order fourteen and requires the independent existence of
C7 and sh. This group is denoted C7h and not S7.

Conjugate Symmetry Elements and Operations. In the symmetry group of BF3 the
^ ^
sequence of operations C3´-1 ^sv C3 means to rotate by 120 ˚ perform ^sv, then rotate back 120˚.

This sequence of operations is equivalent to reflection in a plane rotated 120˚ from the initial
^ ^
one, as shown below. The similarity transformation ( C32)-1 ^sv C32 generates an operation, which
is the third vertical mirror plane. The three equivalent sv symmetry operations belong to the

same conjugate class. Symmetry equivalent symmetry operations (i.e., operations belonging to
symmetry elements that are interchanged by symmetry operations of the group) belong to the
same conjugate class. In BF3 all the operations associated with the equivalent C2 elements
^ ^ ^
belong to the same class. This may be verified by the similarity transformations C3-1 C2 C3 and
^ ^ ^
( C32)-1 C2 C32 operating on any of the three C2 axis.

22
 23

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are possible. Consider the planar ion PtCl42-, which contains one four-fold axis normal to the
molecular plane and four perpendicular C2 axis as shown. Clearly the pair of axis labeled C2´

C2"
C2' C2'

Cl Cl

Pt C2"

Cl Cl y

x currentpoint 192837465
are equivalent, as are the pair of axis C2" since the four-fold rotation interchanges elements
among the pairs; however, the C2´ and C2" axis are not equivalent. There is no operation that
will interchange these elements. Primes designate C2 axes perpendicular to an even principal
^ ^
axis. The C42 operation associated with the four-fold axis is called C2. You might be surprised
to find that a C4 axis and one perpendicular C2´ axis generate the remaining three "primed" two-
^ ^
fold axes. Action of C4 on one C2´ axis generates the other C2´ axis. With the application of C4
^ ^ ^
or C2 no new axes are generated; however, consider the product of operators C4 C2´ acting on
the point (x,y,z). Take one C2´ axis to lie along the x axis and choose C4 coincident with the z

23
 24

^ ^
axis. The operation C2´ on the general point (x,y,z) produces a new point at (x,-y,-z). The C4
^
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y
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^
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• 4
x
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^
C2" axis bisecting the xy quadrant of the coordinate system because C2" (x,y,z) ≠ (y,x,-z).
136
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C2"
(x,y,z)
• x

^ ^ ^
This proves that the combination of a C2´ operation with C4 generates the C2" operation, and
^
that the two C2´ belong to the same conjugate class. You may prove that the two C2" comprise a

second class.
There are likewise two classes of vertical reflection planes. The two planes containing
the C4 axis and one C2´ axis are called s v. Those mirror planes containing the C2" axis are
denoted sd. This illustrates an interesting consequence of a vertical reflection plane. Consider
the effect of ^sv or ^sd on rotation around the principal axis. The effect of ^sv is to change the

sense of

sv

Cnm Cn-mcurrentpoint 192837465

24
 25

rotation from counterclockwise to clockwise. This means that rotation by 360˚/n and -360˚/n are
^ ^
equivalent. In other words a rotation Cnm and its inverse Cn-m belong to the same conjugate
class when a mirror plane contains the rotation axis. For example, the operations of a C7 axis
fall into the classes (C7, C76); (C72, C75); (C73, C74) and for a C6 axis the classes are (C6, C65);
(C3, C32); (C2) when a sv or sd mirror plane also exists.

Molecular symmetry groups. When you search for molecular symmetry elements, look
for rotations, reflections and rotoreflection elements, which interchange equivalent atoms in a
molecule and leave others untouched. The short hand notation for the various point groups uses
abbreviations, which often specify the key symmetry elements present. The complete set of
symmetry operations of a molecule defines a group, since they satisfy all the necessary
mathematical conditions. When confronted with a molecule whose symmetry group must be
determined, the following approach can be used.
Special symmetry groups usually are self-evident. The group D•h is the point group of

homonuclear diatomic molecules and other linear molecules that possess a sh plane (e.g., CO2).
For linear molecules an infinite number of sv planes always exist. The symbol D in a group

name always means that there are n-two-fold axes perpendicular to the n-fold principal axis. The
presence of sh and sv planes in a molecule always requires the presence of n^C´2 axes, since
^
one can show that ^sh ^sv = C´2; however, the converse is not true. Therefore, there are an infinite
number of C2 axes perpendicular to the C• axis of the molecule. The C• axis and sh generate
^
an infinite number of S•f operations; one is S2 = î.

If a linear molecule does not contain a sh plane, e.g., HCl or OCS, then it belongs to the
C•v point group. This point group contains a C• axis and an infinite number of sv planes.
Clearly C•v is a proper subgroup of D•h.

A free atom belongs to the symmetry group Kh, which is the group of symmetry

operations of a sphere. We shall not be concerned with this point group; however, a

25
 26

consequence of spherical symmetry is the requirement that the angular wavefunctions of atoms
behave like spherical harmonics.

There are seven special symmetry groups, which contain multiple high order (Cn, n > 3)

axes. These are the only possibilities for 3-dimensional objects. The groups may be derived
from

octahedron tetrahedron cube

Oh Td Oh
3 C4 4 C3 3 C4

dodecahedron icosahedron

Ih Ih
12 C 5 axes 12 C 5 axes

Figure 1.16. The Five Platonic Solids and Their Point Groups,
with The High Order C n Axes Listed.

26
 27

the symmetry operations of the five Platonic solids (octahedron, tetrahedron, cube, icosahedron,
dodecahedron). Platonic solids are solids, shown in figure 1.16, whose edges and verticies are
all equivalent and whose faces are all some regular polygon. The symmetry operations of the
tetrahedron comprise the group Td. The cube and octahedron possess equivalent elements and
their operations define the Oh group.
The pentagonal dodecahedron and icosahedron likewise define Ih. We will restrict our
discussion to the Oh group and its subgroups, O, Td, Th, and T, since Ih and its subgroup I are
encountered less frequently. The collection of groups {O, Td, Th, and T} are often referred to as
cubic groups. The symmetry elements belonging to an octahedron are: three C4 axes that pass
through opposite verticies of the octahedron; four C3 axes that pass through opposite triangular
faces of the octahedron; six C2 axes that bisect opposite edges of the octaedron; four S6 axes
coincident with the C3 axes; three S4 axes coincident with the C4 axes; an inversion center or S2
axis coincident with C4; three sh which are perpendicular to one C4 axis and contain two others.
Therefore, a single plane defined as sh, also can be thought of as sv with respect to the other C4
axis. Similarly, there are six planes called s d, which are also s v planes containing a C3 axis.
Subgroups of Oh are generated by removing the following symmetry elements:

O = lacks i, S4, S6, sh and sd and is called the pure rotation subgroup of Oh.
Td = this group lacks C4, i and sh and is the group of tetrahedral molecules, e.g., CH4.
Th = this uncommon group is derived from Td by removing S4 and sd elements.
T = the pure rotation subgroup of Td contains only C3 and C2 axes.

If a molecule belongs to none of these special groups, then focus on the highest order
rotation axis. Those rare molecules that possess only one n-fold rotation axis and no other
symmetry elements belong to the Cn symmetry group, which is cyclic. If only a rotation axis
exists and no mirror planes or other elements are obvious, a last check should be made for an Sn
axis of order higher than the obvious rotation axis. When a higher order Sn axis can be found,

27
 28

^
then the Sn groups (n = even) are obtained. Naturally n must be even since Snn = ^sh when n is
odd and both Cn and s h exist independently. These groups (n = odd) are conventionally
designated Cnh. Also, when n = 2, the S2 group (remember S2 = i) is conventionally called Ci.
If we add to a Cn group nsv (n odd) or n/2sv and n/2sd (n even) mirror planes, but no other
rotation axes, then the Cnv groups are generated. If to the elements of Cn we add a horizontal
^
mirror plane, then we generate the Cnh groups. The product of Cn and ^sh also generate an Sn

symmetry element and its associated operations.

When additional n-two-fold axes perpendicular to Cn are present, but no mirror planes,
then the Dn groups are generated. Addition of a sh plane to the rotation symmetry elements of a
Dn group generates the D nh groups. Similar to the Cnh groups an Sn symmetry axis is also
^
produced (if n is even an inversion center will be present). The product C ^s (where C is
2 h 2

associated with n ^ C2 axes in the D nh group) generates vertical mirror planes so that the Dnh
group also contains nsv planes (n odd) or n/2sv and n/2sd planes (n even). If in addition to the
elements of a Dn group an S2n axis is present, then the Dnd groups are obtained. The product
^
S^n C2 (C2 belongs to a C2 axis perpendicular to the n-fold axis) yields the operation ^s so that an
d

additional n dihedral mirror planes are required.

If a molecule contains as the only symmetry element a mirror plane, then the group is
called Cs. Finally, if no symmetry elements, other than E, exist, then the molecular symmetry
group is the trivial one called C1. Table I.1 summarizes the groups we just discussed and their

associated elements. It provides a useful reminder of all the necessary elements when assigning
symmetry point groups.

28
 29

Table 1.1 Common Point Groups and Their Symmetry Elements

Point Group Symmetry Elements Present

C1 E
Cs E, sh
Ci E, i
Cn E, Cn
Dn n = odd E, Cn, n^C2
Dn n = even E, Cn, n/2^C2´, n/2^C2´´
Cnv n = odd E, Cn, nsv
Cnv n = even E, Cn, n/2sv, n/2sd
Cnh n = odd E, Cn, sh, Sn
Cnh n = even E, Cn, sh, Sn, i
Dnh n = odd E, Cn, sh, n^C2, Sn, nsv
Dnh n = even E, Cn, sh, n/2^C2´, n/2^C2´´, Sn, n/2sv, n/2sd, i
Dnd n = odd E, Cn, n^C2, i, S2n, nsd

Dnd n = even E, Cn, nC2´, S2n, nsd

Sn n = even only E, Sn, Cn/2 and i if n/2 odd

T E, 4C3, 3C2
Th E, 4C3, 3C2, 4S2n, i, 3sh
Td E, 4C3, 3C2, 3S4, 6sd
O E, 3C4, 4C3, 6C2
Oh E, 3C4, 4C3, 6C2, 4S6, 3S4, i, 3sh, 6sd
I E, 6C5, 10C3, 15C2
Ih E, 6C5, 10C3, 15C2, i, 6S10, 10S6, 15s
Kh E, infinite numbers of all symmetry elements

29
 30

1.4 Site Symmetry of Molecules and Ions in Solids

Most of the elements, as well as most inorganic compounds, exist as solids. The ideas
about symmetry point groups can be applied to molecules or ions in crystal lattices in the context
of site symmetry and pseudosymmetry. A crystal results from the periodic repetition of a
specific arrangement of atoms through space. For a regular infinite array of objects the act of
translation in space can be a valid symmetry operation, in addition to those described previously.
Consider the infinite one-dimensional lattice
---,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,---
Translation to the right or left by an integral multiple of the lattice spacing yields an
indistinguishable physical configuration. This operation is important in considering atomic
arrays in crystals. Seven three dimensional boxes (or parallelpipeds) used to summarize three-
dimensional packing are given in Table I.2. Each box can be classified by the lengths of its three
edges a, b, and c, which are assigned using the convention for a right-handed coordinate system.
_____________________________________________________________________________
Table I.2: The Seven Crystal Systems

System Conditions on Cell Parameters Lattice Symmetry

_
triclinic a ≠ b ≠ c; a ≠ b ≠ g Ci or 1
monoclinic a ≠ b ≠ c; a = g = 90˚, b > 90˚ C2h or 2/m
orthorhombic a ≠ b ≠ c; a = b = g =90˚ D2h or mmm
tetragonal a = b ≠ c; a = b = g = 90˚ D4h or 4/mmm
_
trigonal (rhombohedral setting)* a = b = c; a = b = g ≠90˚ D3d or 3 m
hexagonal a = b = c; a = b = 90˚; g = 120˚ D6h or 6/mmm
cubic a = b = c; a = b = g = 90˚ Oh or m3m
_____________________________________________________________________________
*A hexagonal setting is also possible.

The angles between the vectors are defined as a = between b and c, b = between a and c and g =

between a and b. These unit cells summarize the fundamental packing patterns possible in

30
 31

solids. The rightmost column in this table lists the symmetry point group of the crystal system in
conventional (Schoenflies) notation, along with the Hermann-Maugin equivalent used by
crystallographers and solid state chemists. In the latter notation Cn rotation axes are denoted by
n, mirror planes by m and sh mirror planes are denoted n/m. An inversion center is specified by

a bar above the principal rotation axis. In a formal approach to space groups the addition of
centered lattices and the possible subsymmetries within each unit cell would be developed to
yield the 230 space groups. For an excellent discussion of these considerations we recommend
the text by Stout and Jensen listed in the references for this chapter. Extensive tabulations for the
symmetry elements of each space group can be found in the reference work, International Tables
for X-ray Crystallography, available in most libraries. The discussion here will be limited to the
relation between the lattice symmetry for the solid and the point group symmetry of an
individual ion or molecule in the unit cell.
It is important to recognize that for molecules in crystals there is not necessarily a
correlation between molecular symmetry and the symmetry of the unit cell. Highly symmetrical
molecules may crystallize in low symmetry unit cells and molecules of low symmetry may

crystallize in unit cells of high symmetry. Atoms, molecules, or ions in a crystal may occupy
two types of positions in a unit cell. The first is called a general position, which exists for all
unit cells. There is no crystal symmetry associated with a general position. When a high

symmetry molecule, e.g., an octahedral metal complex, occupies a general position then it
rigorously possesses no symmetry because the environment of the crystal about it is asymmetric.
The asymmetry of the local environment distorts the site symmetry to C 1 or 1; however, an

octahedral pseudosymmetry remains. The low symmetry crystal environment can often be
detected spectroscopically from a splitting of degenerate E or T energy levels. Perturbation of a
molecule's symmetry in the crystal from its isolated symmetry, as in the gas phase, may be great
or small. The magnitude of the perturbation depends on the strength of interactions between the
molecule and its environment. In a molecular crystal, where the forces will primarily be Van der
Waals in nature, the deviation from the idealized gas phase molecular symmetry will be small.

31
 32

In ionic crystal, where strong electrostatic forces are present, the distortion of the idealized
symmetry is expected to be greater.
The other kind of position in a unit cell is called a special position. These special
positions generally have unit cell (x, y, z) coordinates of 0, 1/2, 1/4, or 1/3 and are listed for each
space group in the International Tables for X-ray Crystallography. When a molecule or ion
occupies a special position then it possesses a rigorous site symmetry, which is determined by
the crystal environment. Several different site symmetries are possible in a unit cell, the highest
being the maximum symmetry of the cell. Thus cubic unit cells may have special positions of
Oh symmetry, which an octahedral molecule could occupy. If an octahedral molecule occupies
such a position, then the symmetry is rigorously Oh and splitting of degenerate energy levels by

a low symmetry crystal environment does not occur. Coupling between molecules in the unit
cell may, however, give exciton splittings, as noted later.
A simple example illustrates the essential points. Consider the case of triclinic crystals.
_
Two space groups are possible. One, denoted P1 , has the maximum symmetry indicated in
_
Table I.2. The other P1, a subgroup of P1 , has no symmetry. In P1 every position in the unit

cell has a crystal environment with complete asymmetry. There is generally only one molecule
(more rigorously 1 asymmetric unit since a pair or e.g., a hydrogen bonded cluster of molecules
_
can sometimes form a packing unit) per unit cell in this space group. In P1 , which possesses an

inversion center at the origin of the unit cell, an arbitrary point or general position (x, y, z) is
transformed to (-x, -y, -z) by the inversion operation. Thus, there must be two molecules
(asymmetric units) per unit cell if they occupy a general position. It is possible for molecules
that contain an inversion center to occupy the special position (0. 0, 0). Then there need be only
one asymmetric unit per cell, with the added condition that it possess rigorous inversion
symmetry. Similar conditions hold for higher symmetry space groups, but the basic concept
resembles that illustrated above.
Another concern, beyond that of the site symmetry in a crystal, is the possibility of
coupling between asymmetric units in a crystal. In ionic solids the forces that interconnect all

32
 33

the asymmetric units in a cell makes it imperative that these couplings be considered if one wants
to understand vibrations in the solid state. Even molecular crystals can exhibit unusual splittings
from such phenomena. One example occurs for coupling between excited states in crystals and
this is often referred to as exciton coupling. For example, the excited states q1 and q 2 of two
_
asymmetric units in P1 could interact to yield composite sum and difference net states (q1 + q2
and q1 - q2). In this way a single excited state of the isolated molecule gives rise to two crystal

states of different energy. The student with a serious interest in solid-state spectroscopy will
need to delve into this in more detail. For most readers this section serves as a caveat should
they attempt to interpret spectra of solids.

33
 34

Additional Readings:
Atkins, P. W.; Child, M. S.; Phillips, C. S. G. Tables for Group Theory; Oxford University Press:
London, 1970.
Bunker, P. R. Molecular Symmetry and Spectroscopy; Academic Press, New York, 1979.
Burdett, J. K. Molecular Shapes: Theoretical Models of Inorganic Stereochemistry; Wiley:
New York, 1980.
Burns, G. Introduction to Group Theory with Applications; Academic Press: New York, 1977.
Cotton, F. A. Chemical Applications of Group Theory; 2nd Ed., Wiley-Interscience: New York,
1971. A good introduction for chemists, with many worked examples.
Donaldson, J. D.; Ross, S. D. Symmetry and Stereochemistry; Wiley: New York, 1972.
Describes space groups and solid state symmetries.
Dorain, P. B. Symmetry in Inorganic Chemistry; Addison-Wesley: Reading, Mass., 1965.
Fackler, J. P., Jr. Symmetry in Chemical Theory; the Application of Group Theoretical
Techniques to the Solution of Chemical Problems; Dowden, Hutchinson and Rossi:

Stroudsburg, Pennsylvania, 1973.

Fackler, J. P., Jr. Symmetry in Coordination Chemistry; Academic Press, New York, 1971.
Ferraro, J. R.; Ziomek, J. S. Introductory Group Theory and its Application to Molecular

Structure; 2nd Ed., Plenum Press: New York, 1975.

Griffith, J. S. The Irreducible Tenson Method for Molecular Symmetry Groups; Prentice-Hall:
Englewood Cliffs, New Jersey, 1962.
Hall, L. H. Group Theory and Symmetry in Chemistry; McGraw-Hill: New York, 1969.
Hamermesh, M. Group Theory and its Application to Physical Problems; Addision-Wesley:
Reading, Massachusetts, 1962. A rigorous mathematical development with advanced
applications to atomic and nuclear energy levels. Develops symmetric and continuous groups
as well as irreducible tensor methods.
Hochstrasser, R. M. Molecular Aspects of Symmetry; W. A. Benjamin: New York, 1966.

34
 35

Jaffe, H. H.; Orchin, M. Symmetry in Chemistry; R. E. Krieger Pub. Co.: Huntington, New
York, 1977.
Kettle, S. F. A. Symmetry and Structure; Wiley: New York, 1986.
Lax, M. J. Symmetry Principles in Solid State and Molecular Physics; Wiley: New York, 1974.
McWeeny, R. Symmetry; An Introduction to Group Thoery and its Applications; Pergamon
Press: Oxford, 1963.
Piepho, S. B.; Schatz, P. N. Group Theory in Spectroscopy: With Applications to Magnetic
Circular Dichroism; Wiley: New York, 1983.
Schonland, D. S. Molecular Symmetry: An Introduction to Group Theory and Its Uses in
Chemistry; Van Nostrand: Princeton, New Jersey, 1965.
Slater, J. C. Symmetry and Energy Bands in Crystals; Dover: New York, 1972. Applications of
Group Theory to Wavefunctions of Crystalline Solids.
Stout, G. H.; Jensen, J. H. X-ray Structure Determination: A Practical Guide; 2nd Ed., Wiley:
New York, 1989. Contains a discussion of crystal symmetries with applications to X-ray
crystallography.

Tinkham, M. Group Theory and Quantum Mechanics; McGraw-Hill: New York, 1964. A
concise development of theory with applications to atomic, molecular, and solid state
electronic wavefunctions.

Vincent, A. Molecular Symmetry and Group Theory: A Programmed Introduction to Chemical

Applications; Wiley: New York, 1977.
Wells, A. F. Structural Inorganic Chemistry, 5th ed., Clarendon Press: Oxford, 1984.
Wherrett, B. S. Group Theory for Atoms, Molecules, and Solids; Prentice-Hall International:
Englewood Cliffs, New Jersey, 1986.

35
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36

1.6 Problems
1) Determine which of the following are groups. For those, that are not groups, specify the
missing conditions.
a) The set of all positive integers with group multiplication defined as normal addition.
b) The set of all integers (± and 0) with group multiplication defined as normal addition.
c) The set of all integers (± and 0) with group multiplication defined as normal
multiplication.
2) Prove that all groups of prime order are isomorphic to the cyclic group of that order.
3) Give the point group to which the following molecules belong.
a) MnO42- c) WF6
b) Rh6(CO)16 d) Mo6Cl12 (8 face capping, 4 terminal Cl)

e) methane f) cubane
g) benzene h) Mn2(CO)10
i) Re2Cl82- j) OsCl4N-
k) H2S l)

H B H
N N

B B
N

H currentpoint 192837465
(planar conformation ignore H
on carbons)
m) Co(en)33+ n) cis-MoCl2(CO)4
o) trans-MoCl2(CO)4 p) fac-Mo(CO)3(PPh3)3 (coordination symmetry only,

i.e., ignore Ph groups)

q) mer-Mo(CO)3(PPh3)3 r) Al2Cl6
s) BrCl2F t) CO2

36
 37

u) S8 (cyclic crown structure) v) PPh3 (with propeller conformation of phenyl rings)

w) HOCl x) cyclo-(BCl)4(NCH3)4
y) Ce(NO3)62- (the coordination environment of Ce is icosahedral-each nitrate is bound in

a
planar bidentate fashion such that trans NO3- groups are eclipsed).
z) PF5

4) Consider the 2-dimensional packing of regular polygons of three-fold through eight-fold

symmetry. Which ones can form a close-packed planar network with no overlapping or
gaps in the plane?
5) Based on work in 4 what are the allowed rotational symmetry axes in unit cells of 3-
dimensional crystalline solids?
^
6) Consider the S2 operation around the z axis. Show that its effect on the vector (x, y, z) is

the same as the inversion operation.

37
 38

Key to Problems
1) a) Not group - identity element missing and inverse missing.
b) Yes
c) Not group - inverse elements missing.
2) Proof: Consider how one generates a group of prime order. Lagrange's theorem tells us
the elements of a group must be an integral divisor of the order of the group. If n = prime
then the elements are of order n. Since the # of elements = n, then one element a, and its
powers generate the group
a, a2, ..., an
This is just the cyclic group of order n. Q.E.D.
3) a) Td; b) Td; c) Oh; d) Oh; e) Td; f) Oh; g) D6h; h) D4d; i) D4h; j) C4v;k)
C2v; l) C3h; m) D3; n) C2v; o) D4h; p) C3v; q) C2v; r) D2h; s) C1; t) D•h; u) D4d;

v) C3; w) Cs; x) S4; y) Th; z) D3h

4) It is possible to pack triangles, squares, and hexagons in a close packed 2-dimensional array
but not pentagons: See figure on following page.
^ ^
5) C2, C3, C4, and C6; note: the C4 requires the possibility of C42 = C2.

38
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39