CHAPTER 1

Fundamental Concepts

Our focus in this text wiIl be the application of symmetry arguments to solve
physical problems of chemical interest. As a first step in any application of
this sort, we must identify and catalogue the complete symmetry of the sys-
temo Once this is done, we can employ the mathematics of groups to simplify
the physical problem and subsequently to obtain chemically useful solutions
to it. The advantages of this approach, relative to "brute force" techniques,
tend to increase as the symmetry of the system increases. When the system
has a high degree of structural regularity, complex problems can ha ve ele-
gantly simple solutions. Even in seemingly simple cases, symmetry arguments
rnay provide insights that are difficult to achieve with other approaches.
We will confine our discussion to physical problems of isolated molecules
or complex ions. This means that we will only need to consider the syrnme-
try of the species itself, and not any symmetry that may exist as a result of as-
sociations with neighboring molecules. In generaI, the results we wiIl obtain
will be correct for samples of dilute gases, where intermolecular forces and
influences are negligible. To a lesser extent, the results may be valid for certa in
liquid samples and dilute solutions. However, in these cases observed behavior
may depart significantly from predictions based on the symmetry of the iso-
lated molecules. Sometimes these departures are, in fact, structurally revealing.
In the case of solids, especially ionic crystals and network solids, associa-
tions between individuaI molecules and ions may be considerable, and results
based on individuai symmetries are least likely to be correct. Interaction be-
tween the oriented molecules or ions, and the regularity of the solid itself,
result in new kinds of symmetry relationships not found in isolated species.
An introduction to the symmetry of solids (space group symmetry) is beyond
the intent of this book, but can be found in introductory texts dealing with
crystallography or structure determination by x-ray diffraction. Nonetheless,
the principles we will explore in relation to problems of isolated molecular
species wiU provide a foundation for later study of applications based on crys-
tal symmetry.

1.1 Symmetry Operations and Elements

The symmetry of molecules is defined in terms of symmetry elements and
symmetry operations. A symmetry element is an imaginary geometrica I entity
such as a line, piane, or' point about which a symmetry operation can be per-

•
 2 Chapter 1 Fundamental Concepts 1.1 SymmetryOperations and Elements 3

formed. A symmetry operation is a movement of an object about a syrnme- ation repeatedly, eventually you may bring the object back to the identical
try element such that the object's orientation and position before and after (not simply equivalent) orientation from which you started. Normally, we will
the operation are indistinguishable. This means that the operation carries want to designate the results of successive or compound operations by their
every point of the object into an equivalent point or back into the identical most direct single equivalents. Thus, if a series of repeated operations carries
point. the object back to its starting point, the result would be identified simply as
Another way of determining whether a particular symmetry exists for an identity, This will become clearer as we examine the results of sequential sym-
object is to perform the following test. Observe the object, and then turn metry operations throughout this section.
away while someone performs the symmetry operation. When you turn around The operation of rotation is designated by the symbol C"' indicating that
and observe the object again, you should not be able to tell whether or not rotation about an axis by 271'/n radians (3600/n) brings the object into an
the symmetry operation was actually performed. Note that the object need equivalent position. The value n of a C; rotation is the order of the rotation.
not be in the identical position it had before the operation (although it may It is common to refer to the operation as an n-fold rotation and to refer to
be). It is only necessary that the position be indistinguishable and therefore the corresponding element as an n-fold rotational axis. Sometimes the term
equivalent for the object to possess the particular symmetry. proper axis is used to refer to the element associated with rotation, distin-
To appreciate the difference between indistinguishable and identical po- guishing it from an improper axis, discussed later in this sectìon. For exam-
sitions, try the following exercise. Make a square cutout from stiff paper (e.g., pIe, C4 indicates a fourfold rotation, by which rotation through 271'/4 == 90°
card stock). Label the corners A, B, C, and D. Turn the labeled side down on brings the object into an equivalent position, indistinguishable from the start-
a piece of wood or heavy cardboard, and piace a thumb tack in the middle, ing configuration.
so that the cutout spins freely. Check the identities of the corners in the start- Figure 1.1 shows the effects of successive fourfold rotations about an axis
ing position, and then give the cutout a spino Square it up so that the blank perpendicular to the piane of a planar MX4 molecule. The four identical X
side appears to be in the same orientation as it was before spinning. Now atoms have been labeled XA, XB, Xc, and XD (i.e., XA = XB = Xc == Xo) so
check the identities of the corners. If they are the same as before, the posi- that we can follow the results of each operation. Of course, without these la-
tion is identical to the starting position. Otherwise, the position is simply in- bels the atoms are indistinguishable, and the result of this (or any) symmetry
distinguishable. Note that without the labels, when viewed from the blank operation would be indistinguishable from the starting positions. In the fig-
side, you cannot tell an indistinguishable orientation from the identical (orig- ure we have arbitrarily defined the rotations in a clockwise manner, but we
inai) one. could just as well have defined them in the opposite direction, It is only nec-
The symmetry of a molecule or ion can be described in terms of the com- essary that we be consistent in defining successive rotations about the same
plete collection of symmetry operations it possesses. The total number of op- axis. Notice that carrying out two successive C4 rotations about the same axis
erations may be as few as one or as many as infinity. Regardless of the num- (which we could designate C~) has the same effect as a single C2 rotation
ber of operations, all will be examples of only five types. These are (1) a (271'/2 == 180°), Normally, the simpler notation, C2, would be preferred. If we
seemingly trivial operation called identity, (2) rotation (sometimes called continue with a third C4 rotation, we arrive at a new equivalent configuration,
proper rotation), (3) reflection, (4) inversion, and (5) a two-part operation which is the same as we would have obtained by a single fourfold rotation in
called rotation-reflection (or improper rotation). The elernents about which the opposite direction (here, counterclockwise). To avoid ambiguity, this is
these operations are performed are, respectively, (1) the object itself, (2) a designated cl, meaning three successive fourfold rotations in our chosen di-
line (rotation axis or proper axis) , (3) a piane (reflection piane or mirror rection, In generai, any Cn rotation carried out n-l times will have the same
plane], (4) a point (inversion center or center ofsymmetry), and (5) a line (im- effect as a Cn rotation in the opposite direction. If we designate a counter-
proper axis or alternating axis). Ali the corresponding symmetry elements will clockwise n-fold rotation as c;', then we may write in genera! C~-l == C;;1;
pass through a common point at the center of the structure. For this reason, for example, cl = Ci1,* Finally, if -wé perform a fourth C4 rotation, our MX4
the symmetry of isolated molecules and ions is called point group symmetry. molecule will be brought back into its starting (identical) position. Carrying
The simplest of all symmetry operations is identity, given the symbol E out four successive C4 operations about the same axis is equivalerit to iden-
(or l in older texts). Every object possesses identity. If it possesses no other tity; that is, c1 = E. In generai, any C" rotation carri ed out n times in succes-
symmetry, the object is said to be asymmetric. As an operation, identity does sion will carry the object back into its originaI configuration; that is, C~ = E.
nothing to the molecule. It exists for every object, because the object itself Thus, as shown in Fig. 1.1, this single element, a C4 axis, isassociated with
,exists. The need for such an operation arises from the mathematical require- three unique symmetry operations: C4, C~ == C2, C~ == Cil The fourth op-
ments of group theory, as we shall see later, Of more immediate concern,
identity is often the result of carrying out a particular operation successively *For additional verification of this relationship, try demonstrating that c. = Ci3 and C2 = Ci'
a certain number of times. In other words, if you keep doing the same oper- in Fig, 1.1.
4 Chapter l Fundamental Concepts 1.1 Symmetry Operations and Elements 5

also exists a C2 axis collinear with the C4 axis. These two axes (C4 and C2)
are not the only rotational axes of MX4. There are four other C2 axes in the
piane of the molecule, as shown in Fig. 1.2. These twofold axes are distin-
guished from the previously defined C2 axis by adding prime (') and double
prime (") to their symbols. In generai, when two or more axes of the same n-
fold order exist, the axis or axes collinear with the highest-order axis or axes
XD in the system are designated without modification. Ali others of the same n-
I Iold order are distinguished by adding prime or double prime notations. In
X -M-X
c I A the present case, the two C2 axes are defined so as to pass through more
XB atoms than the two C2 axes. Only two notations are needed for the four axes,
because both C2 axes belong to the same class, while the two C2 axes belong
~C4 to a separate class. We will define the concept of class more generally later,
but for now note that the two C2 axes are geometrically equivalent to each
other and distinct from the Cz axes, which are likewise geometrically equiva-
lent to each other and distinct from the two C2 axes. In listing the complete
set of symmetry operations for a molecule, operations of the same class are
designated by a single notation preceded by a coefficient indicating the num-
ber of equivalent operations comprising the class. For square planar MX4, the
rotational operations grouped by class are 2C4 (C4 and C~), Cz (collinear with
C4), 2C2, and 2C2.
The highest-order rotational axis an object possesses (i.e., the C; axis for
which n is greatest) is called the principal axis of rotation. In some highly sym-
metrical systems (e.g., tetrahedron, octahedron), there may be more than one
principal axis, but most Iess syrnmetrical systems with rotational symmetry
XA will have only one. For planar MX4, the principal axis is the C4 axis, about
I which the operations of C4 and C~ are performed.
X -M-X The operation of reflection defines bilateral symmetry about a piane,
D I B

Xc
called a mlrror plane or reflection piane. Accordingly, if a molecule possesses
Figure 1.1 Successive C4 clockwise rotations of a planar MX4 molecule about an a mirror plane, it will be bisected by that piane. The symbol for the reflection
axis perpendicular to the piane of the molecule (XA = XB = Xc = XD)· operation and its corresponding elernent (the minor piane) is lowercase
sigma, (l'. If the operation of reflection exists, for any point a distance r along
a normal to the minor piane there wiU be an equivalent point at a distance
eration, C:, is just a repeat of identity, E. The C4 and C~ rotations are often -r (cf. Fig. 1.3).
described as two C4 rotations, where it is understood that one rotation is
taken in a clockwise sense, and the other is taken in a counterclockwise sense.
As this example shows, the symbol far carrying out m successive n-fold
rotations of 3600/n about a single axis is C;;', where the result is the same as
a single rotation by (m/n)2n = (m/n)360°. To express the compound rotation
as its simplest equivalent, m and n are written such that the fraction m/n is in
its lowest form; for example, C~ = Cz, c2 = C~, C~ = C~. Furthermore, ro-
tations beyond full circle are expressed as the equivalent single rotation that
is less than 27T = 3600. For example, C~ is a rotation by 450°, equivalent to a
90° rotation about the same axis; that is, C~ = C4·
As we have seen, carrying out two C4 operations in succession about the Figure 1.2 The C:2 and C2 axes of a planar MX4
same axis is the same as C2. In a formai sense, then, we may say that there molecule.

a
 6 Chapter l Fundamental Concepts 1.1 Symmetry Operations and Elements 7

-r

Figure 1.3 Two points, equidistant from a mirror piane

CT, related by reflection.

Figure 1.4 shows the five mirror planes found in a square pIane, such as
a planar MX4 molecule. The five planes are grouped into three classes: oi;
2(Jv, and 2(Jd' As with the C2 axes of planar MX4, the class groupings of the
three kinds of mirror planes can be justified on geometrical grounds, Notice
that ali mirror planes pass through a common point at the center of the mol-
ecule.
Figure 1.S shows the effects of the reflection operations of these mirror
planes. As in Fig. 1.1, the four identical X atoms have been labeled XA, XB,
Xc, and Xn to show the effects of the operations. At first glance, the opera-
tion of (Jh appears to do nothing to the molecule, because it lies entirely
within the mirror pIane. However, if each of the five atoms had a directional
property perpendicular to the plane (e.g., pz orbitals, or vibrationaI motions
of the atoms), the operation of (J;, would transform the property into the neg-
ative of itself, The effect of either a; operation is to leave two trans-related
Xc
------
-.
M~--

Xs XA

Figure 1.5 Effects of reflections of a planar MX4 molecule (XA = XB = Xc = XD).

X atoms and the M atom unaffected and to transpose the other two trans-
related X atoms, which lie on either side of the vertical piane. The effect of
either (Jd operation is to exchange both pairs of X atoms across a dihedral
piane, leaving the M atom unaffected.
Note that for any mirror piane, performing two successive refIections
about the same piane brings the object back into its originai (identical) con-
figuration; that is, (J(J = ~ = E. Thus, any mirror piane is associated with
only one operation, unlike a rotational axis, which may be a common element
for a series of operations.
x :::::-......-.::-:-:-=::::=:!=;::x The notation for the planes in planar MX4 is typical of the notation in
-----M ----
X "",+=--_"-..~X other systems with severa l minor planes in various orientations. A (Jh piane
(horizontal mirror piane) is, defined as perpendicular to the principal axis of
rotation. If no principal axis exists, (Jh is defined as the piane of the molecule.
A o; piane (vertical mirror piane) and a (Jd piane (dihedral mirror piane) are
,.,.
Figure 1.4 Mirror planes of a square planar molecule MX4. ',,>.(, ~;~',.' ,.... defined so as to contain a principal axis of rotation and to be perpendicular
8 Chapter 1 Fundamental Concepts 1.1 Symmetry Operations and Elements 9

to a CF" piane, if it exists. When both CFv and CFd occur in the san:e system, the
distinction between the types is made by defining CFv to contam the greater
number of atoms or to contain a principal axis of a reference Cartesian co-
ordinate system (x or y axis). Any CFd planes typically will contain bond angle Figure 1.6 Effect of inversion (i)
bisectors. In cases with only one type of vertical piane, either CFv or CFd may on an octahedral MX6 molecule
be the conventional notation, depending on the total symmetry of the mole- (XA = XB = Xc = Xo = XE = XF)·
cule. Far example, in the eclipsed conformation of ethane the three vertic~l
mirror planes, which intersect along the C3 axis of the molecule and contam Another, even less restricted, ex ampie is ethane in the staggered config-
the two carbon atoms and two hydrogen atoms (one on each end), are C0n- uration (Fig. 1.7). The inversion center is at the midpoint between the two
ventionally designated CFv. In the staggered conformation of ethane the three carbon atoms. The operation of inversion relates the two carbon atoms to
mirror planes, which also intersect along the C3 axis of the molecl~le and con- each other, and it relates pairs of hydrogen atoms on opposi te ends of the
tain the two carbon atoms and two hydrogen atoms, are conventionally des- molecule. Note that there is no inversion center for ethane in the ec\ipsed
ignated CFd. Fortunately, knowing whether a piane is to be called CF.v or CFd in configuration. (Building models of the two conformations may be helpful to
such cases is not crucial to applying symmetry arguments to physical prob- see the difference.)
lems. The conventions become apparent when using the standard tables that Rotation-reflection, as its name implies, is a cornpound operation. It is
list (among other things) all the symmetry operations for a particular system also called improper rotation, to distinguish it from proper rotation, Cn.
(cf. Appendix A). . ., Rotation-reflection consists of a proper rotation followed by a reflection in a
The operation of inversion is defined relative to the centrai p.01~t within plane perpendicular to the axis of rotation. Actually, the arder of performing
the molecule, through which ali symmetry elements must passo This IS usually rotation and reflection in a plane perpendicular to the rotation axis can be re-
taken as the origin of a Cartesian coordinate system. Relative to this system, versed, giving the same result. Most practitioners, however, take their cue
if inversion exists for the molecule, for every point with coordinates (x, y, z) from the name rotation-reflection and perform the two parts of the opera-
there will be an equivalent point at coordinates (-x, -y, -z). The centrai tion in that order. The axis of this operation is called an improper axis. Both
point at (O, O,O), which is the element associated with the inversio.n operation, the operation and the element are given the symbol 5n, where n refers to the
is called an inversion center or center of symmetry. Viewed m a different way, initial rotation by 27T/n = 360o/n.
if inversion symmetry exists, a line drawn from any atom through the center The two parts of an improper rotation (C" and CFh) may be genuine op-
of the molecule will connect with an equivalent atom at an equal distance on erations of the molecule in their own right, but often they-are not. If both a
the other side of the molecule. The point at which al! such connecting lines Cn rotation and a reflection perpendicular to the rotation (CF/z) do exist inde-
intersect is the inversion center. Molecules that have inversion symmetry are pendently, then the improper rotation 5n must also exist, since both its parts
said to be centrosymmetric. are present. For example, in planar MX4, both C4 and CF" exist; therefore, the
Both the element and the operation of inversion are given t~e symbo: i. operation 54 exists. The 54 improper axis in this case is collinear with the prin-
Note that perforrning inversion twice in succession would bnng every point cipal proper rotational axis (C4). However, the presence of both C4 and CF" is
(x, y, z) back into itself, equivalent to identity; that is, ii = P = E. Thus, li.ke not a sin e qua non for the existence of S4' A good example of this can be
a reflection piane, an inversion center has only one operation associated with found in a tetrahedral MX4 molecule, where each X-M-X angle bisector lies
il. Furthermore, since the inversion center is always located at the centrai along an 54 axis. Figure 1.8 shows the effects of the two steps of the 54 oper-
point in the molecule, there can be only one inversion center in any system. ation about one such axis. As before, the four equivalent X atoms have been
Planar MX4 is centrosymmetric. Relative to the starting configurations of
either Fig. 1.1 or Fig. 1.5, inversion interchanges the X atoms labeled XA and
Xc and also those labeled XB and Xo. The centrai M atom, which is located
at the inversion center, is not affected. This ex ampie is somewhat restncted,
since all relations between equivalent points occur within the piane of the Figure 1.7 Ethane in the staggered configuration,
molecule itself (the xy piane). Perhaps a better example, illustrating the The inversion center is at the midpoint along the C-C
three-dimensional character of the inversion operation, is provided by an oc- bond. Hydrogen atoms related by inversion are con-
tahedral MX6 molecule (Fig. 1.6). Bere the equivalent atoms lie equidistant nected by dotted lines, which intersect at the inversion
in positive and negative directions along each of the three axes of the coor- center. The two carbon atoms are also related by
inversion.
dinate system (i.e., :tx, :ty, z z ) .

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lO Chapter l Fundamental Concepts 1.1 Symmetry 0i>erations and Elements Il

XC-~-XA
1 D XD

XC-~-XA
XB xB
l
,
C4 ~54

Xc

B,
X ·"""M'''''..X D XB-~-XD

XA XA

Figure 1.8 54 improper rotation of a tetrahedral MX4

t 54

~c molecule (XA = Xs = Xc = Xo). The improper axis is

perpendicular to the page. Rotation is arbitrarily taken in
1
XA-~-XC
B

XB-~-XD
a clockwise direction. Note that neither C4 nor Uh are gen-
XA uine symmetry operations of tetrahedral MX4. XD

t54

labeled XA, XB, Xc, and XD so that the effects of the operations can be fol- XA
lowed. Notice that neither the C4 step nor the ah step by itself results in a
XD-~-XB
configuration that is indistinguishable (i.e., equivalent) to the configuration
prior to executing each operation. However, the net result of these two steps Xc
in succession leads to a configuration which is, indeed, equivalent to the star t-
ing configuration, if we disregard the artificial A, B, C, D labels.
As these two MX4 cases demonstrate, an 54 axis must exist when C4 and
5-4 1
t 54

~D Figure 1.9 Successive 54 operations on a tetra-

ah exist (e.g., planar MX4), but it may also exist if neither C4 nor ah exist (e.g.,
hedral MX4 molecule (XA = XB = Xc = Xo).
tetrahedral MX4). As an exercise to see these kinds of possibilities in other XC-~-XA
Rotations are clockwise, except 541, which is
cases, you might build models of ethane in both the eclipsed and staggered xB equivalent to the clockwise operation S~.
conformations and examine the effects of their improper rotations. Note that
in the eclipsed conformation there is a C3 axis collinear with the C-C bond
and a ah mirror piane that bisects the C-C bond and lies perpendicular to il. is preferred. A fourth 54 operation results in the originai configuration; that
Therefore, there must be an 53 axis coIIinear with the C3 axis. In the stag- is, 5! = E. Consistent with the convention of designating operations by their
gered configuration there is no ah piane, although the C3 axis persists. simplest notation, only 54 and 5~ are taken as improper rotations. The oper-:
However, there is an 56 axis collinear with the C3 axis, even though neither ations of 5~ and 51 are equivalent to C2 and E, respectively, and are so des-
C6 nor ah exist. ignated. Thus, there are two 54 operations (54 and 5~ = 541) about this axis.
Like proper rotations, a series of improper rotations can be performed Figure 1.10 shows a tetrahedral molecule inscribed in a cube, a useful way
about the same axis. Figure 1.9 shows the results for successive 54 rotations of presenting such molecules, as we Sl1all see throughout this text. From this
about an improper axis of tetrahedral MX4. The direction of rotation (clock- we can see that the three equivalent 54 axes, which lie along the bisectors of
wise or counterclockwise) is unimportant, as long as successive rotation-re- pairs of X-M-X angles, are collinear with the three C2 axes. These axes de-
flection operations are carri ed out in the same direction. Note that succes- fine the x, y, and z directions of a reference Cartesian coordinate system for a
sively carrying out two 54 operations has the effect of a single C2 operation tetrahedral MX4 molecule. In this highly symmetric systemall three directions
about the same axis; that is, 5~ = C2. Thus the 54 axis is collinear with a C2 are equivalent and indistinguishable, which implies that the three 54 improper
axis. Carrying out a third 54 operation, written 5~, results in an equivalent con- axes are geometrically indistinguishable from each other. Each improper axis
figuration, which also could have been reached by a single 54 operation in the has two operations associated with it, 54 and 5~ = 541 Consequently, the
opposite direction (here, counterclockwise), shown as 541 in Fig. 1.9. Keeping three axes give rise to a total of six operations, which belong to a class des-
with the chosen direction of rotation and to avoid ambiguity, the notation 5~ ignated 654 in tabular Iistings of the symmetry of a tetrahedral system.
 12 Chapter 1 Fundamental Concepts 1.2 Defining the Coordinate System 13

fined in the same sense as the thumb, index finger, and middle fingers of the
right hand when extended so that they are mutually perpendicular to each
other. Hold your right hand so that your thumb is pointing up, extend your
index finger as if pointing a gun, and bend your middle finger so that it is per-
pendicular to the other two. Your thumb, index finger, and middle finger now
correspond, respectively, to the z, x, and y directions of the Cartesian coor-
Figure 1.10 A tetrahedral MX4 mole- dina te system (cf. Fig. 1.11). Alternately, take the thumb, index finger, and
cule inscribed in a cube. A C2 axis, middle fingers as x, y, and z. respectively, in which case the palm must be ro-
collinear with an 54 axis, passes through tated face up to present the z axis in its usual perpendicular orientation (cf.
the centers of each pair of opposi te
Fig. 1.11). Either mnemonic gives the same relative axis orientations. These
cube faces and through the center of
orientations are retained regardless of whether the system is shown with the
the rnolecule.
z axis pointing up or in some other orientation.
The orientation of a molecule's bonds and bond angles relative to the co-
The lowest-order improper rotation that is not a simpler operation is S3' ordinate system is often defined on the basis of the symmetry of the mole-
If we were to imagine a hypothetical SI operation, this would be a "onefold" cule. Generally, the following conventions are observed:
rotation (i.e., E) followed by reflection. The first step does nothing, so the net
effect is simply the second step, the reflection. Thus, SI = 0-. If we were to 1. The ori gin of the coordinate system is located at the centrai atom or the
imagine a hypothetical S2 operation, this would be a C2 operation followed center of the molecule.
by a o-h operation. If we define the C2 axis as z. the effect of the first step 2. The z axis is collinear with the highest-order rotational axis (the princi-
would be to convert every point (x, y, z) into an equivalent point at pal axis). If there are several highest-order rotational axes, z is usually
C-x, -y, z). The second step, a reflection across the xy pIane, would trans- taken as the axis passing through the greatest number of atoms. However,
pose every coordinate z into - z: that is, (- x, - y, z) --7 (-x, -y, - z). The net far a tetrahedral molecule, the x, y, and z axes are defined as collinear
effect of the two steps is to convert every point (x, y, z) into an equivalent with the three C2 axes (collinear with the three S4 axes).
point at (-x, -y, - z). This is the single result of an inversion operation, so 3. For planar molecules, if the z axis as deEined above is perpendicular to
S2 = Ì.
the molecular piane, the x axis lies in the pIane of the molecule and passes
For improper axes with n 2:: 3, each S; element generates a series of S" through the greatest number of atoms (e. g., square planar XeF4). If the z
operations. As we have seen with S4, not all of these are uniquely improper axis lies in the piane of the molecule, then the x axis stands perpendicu-
rotations (e.g., S~ = C2, S~ = E). For a series of successive S; operations, the lar to the plane (e.g., bent HzO).
pattern of equivalences with simpler operations depends upon whether n is
even or odd. The following generaI relationships for S:
operations, where 4. Far nonplanar molecules, once the z axis has been defined, the x axis is
usually chosen so that the xz pIane contains as many atoms as possible.
n 2:: 3 and m = 1,2, ... , n, ... , 2n, may be useful at certain points:
If there are two or more such planes containing identical sets of atoms,
1. If n is even, S:: = E.
2. If n is odd, S:: = o- and S,~n = E.
3. If m is even, S:; = C:; when m < n and S:; = c:;-n when m > n.
4. If S; with even n exists, then C"/2 exists.
5. If S; with odd n exists, then both Cn and o- perpendicular to C; exist.

1.2 Defining the Coordinate System

.. In many of our discussions it will be necessary to define acoordinate system
for a molecular species. In all cases we will adopt a standard Cartesian coor-
dinate system with axes x, y, and z defined by the so-called "right-hand rule." Figure 1.11 Two ways of assigning the thumb, index finger, and middle finger of the
By this convention, the positive directions of the three cardinal axes are de- right hand as mnemonics for the axis orientations of a Cartesian coordinate systern.

•
14 Chapter 1 Fundamental Concepts 1.3 Combining Symmetry Operations 15

any one may be taken as the xz piane. Where a decision about the ori-
entation of the x axis cannot be made on this basis, the distinction be-
tween x and y is usually not important or is not generally fixed by con-
vention.
Il is important to realize that these are conventions and not rules. When
comparing texts, you may occasionally find different choices ofaxis orienta-
tion for the same molecular system. In such cases, the quantitative and qual- ~c
itative results based on symmetry arguments will be the same, varying only in XB-~-XD XA-~-XC
the labels used to describe thern. Correlating the differences is generally
XA XB
straightforward. At times it can be useful to choose a nonconventional ori-
entation of the coordinate system in order to emphasize particular relation-
ships between different compounds or different geometries of the same com- s,l
pound.
l"· Figure 1.12 The arder of performing S4
1.3 Combining Symmetry Operations
XD-~-XB •
c2• 1
-
XB-~-XD
A and Uv, shown here far a tetrahedral MX4
molecule, affects the result. The final po-
We have seen that successive application of the same or different symmetry sitions in each case are not the same, but
XA Xc they are related to each other by C2.
operations sometimes has the same effect as a single operation. For exarnple,
performing two S4 rotations in succession about the same axis has the net ef-
fect of a single C2 rotation. Likewise, performing a C4 rotation followed by a ements in Fig. 1.13. The pairs of Br atoms and Cl atoms have been distin-
(Th reflection has by definition the sarne effect as the improper rotation S4. g~ished from one another by subscript a and b (Bra, Br, and Cla, CI b) to fa-
This kind of combination is called multiplication, although in this context the cIlItate. followmg the effects of the operations. The complete set of symmetry
term has a slightly different meaning than in the customary arithmetic sense. operations for the molecule consists of identity (E), a twofold principal axis
The end result of carrying out different operations in succession may de- of rotation (C2), and two reflections about different mirror planes ((Tv and
pend on the order in which they are performed. In other words, combinations (T~). As shown in Fig. 1.13, the two Cl atoms lie in the (Tv plane, and the two
o] symmetry operations do not always commute. For this reason we need to Br atoms lie in the (T: piane. Rather than depict the effect of each operation
adopt a standard way of writing such multiplications so as to imply the order OD the rnolecule, let us introduce a column matrix notation to indicate the po-
of the operations. By convention, combinations of symmetry operations are sitions of atoms before and after each operation. Tbe carbon atom is unaf-
written in a right-to-left order. For example, BA means "do A first, then B." fected by any operation, because it lies at the center point of the systern,
If the result of BA is the same as could be achieved by a single operation X, through WhICb all symmetry elements passo Only the Br and Cl atoms are
then we write BA = X. Thus, S4S4 = C2, and (ThC4 = S4. moved in any operation, so our matrices need only describe the positions of
As an example of noncommutative operations, consider a tetrahedron on
which we perform S4 followed by (Tv, and for comparison (Tv followed by S4
(Fig. 1.12). The final configurations in both cases are indistinguishable, as
they must be for genuine symmetry operations, but the actual positions of the
four equivalent X atoms (labeled XA, XB, Xc, and Xo) are not the same. To
get from one final configuration to the other we must perform a C2 rotation
about the same axis as the S4 improper rotation. Thus, S4(Tv * uv54, but rather
we see that S4(Tv = C2uv54. The fact that commutation is not generally ob-
served does not mean that it is never observed. Indeed, many operations do
commute with one another; for example, C4(Th = UhC4 = 54·
Let us examine the complete set of symmetry operations for a particular
molecule and determine ali the binary combinations of the symmetry opera-
tions it possesses. Our ex ampie will be CBr2CI2, shown with its symmetry el- Figure 1.13 Symmetry elements of CBr2CI2 .

•
16 Chapter 1 Fundamental Concepts 1.3 Combining Symmetry Operations 17

those atoms. Thus, a 1 x 4 rnatrix will suffice to describe the Iocations of twice. For each of these, performing the operation a second time brings the
these four atoms. Each position in the 1 X 4 column matrix should be re ad as molecule back into its originaI configuration, essentially undoing the result of
a particular position in space, occupied by the designated atomo Using this no- the first performance of the operation. Thus, we see EE = E, CzCz = E,
tation, we obtain the following results: a.o ; = E, and (J"~(J"~= E. Among the mixed binary combinations, notice that
any combination with E, either as the first or second operation, gives the
sarne result as the nonidentity operation alone. This must be, since E really
does nothing to the molecule. Thus, we have CzE = ECz = C2, (J"vE = E(J"v =
(J"v, (J"~E = E(J"~ = (J"~.The remaining mixed binary combinations are some-
what Iess obvious.
We can determine the net result of the product Cz(J"v by the following
procedure. First perform o; on the original configuration to obtain an inter-
mediate configuration, and then perform C2 on this configuration to obtain
the finai result. In matrix notation, the first step has the following effect:

From this configuration, we apply C2 to obtain the following effect:

This final configuration is the same as could be achieved by a (J"~ reflection

The symbois [E], [Cz], Iv-l. and [(J"~] represent operator matrices, which act on the originaI configuration of the molecule:
on the original I X 4 matrices to convert them into the matrices that describe
the orientations after the symmetry operations. * We will examine the explicit
mathematicai forms of these kinds of matrices in Chapter 2. At this point we
ne ed only be concerned with the results for CBrzClz. From the matrices
above, we see that (1) identity, E, leaves all atoms in their originaI positions;
(2) the twofold rotation, C2, exchanges Br atoms with each other, and it ex-
changes Cl atoms with each other; (3) the reflection a.; exchanges Br atoms
with each other, but Ieaves the Cl atoms in pIace; and (4) the second reflec- From this we see that CZO"v = (J"~.
tion, (J"~, exchanges Cl atorns, but leaves the Br atoms in pIace. Note that any In the case of these two operations, reversing the order produces the
atom that lies on a particular symmetry element is unaffected by the associ- same finai configuration. Applying the rotation first, we obtain
ated operation.
Now let us consider the results.for binary combinations of these opera-
tions, beginning with combinations in which each operation is performed

*Note that matrix equations are written in the usual mathematical way-that is, left-to-right no-
tation .

•
18 Chapter 1 Fundamental Concepts 1.4 Symmetry Point Groups 19

Following this with a Uv reflection yields Closure. If A and Bare elements of the group G, and if AB = X, then X
is also in the group G. The term "elernent" is used in this context in its math-
ematical sense. The mernbers of any mathematical group are the elements of
the group. In the case of symmetry groups, with which we are concerned here,
the group elements are the symmetry operations, not the symmetry elements.
The symmetry elements associated with the operations in generaI do not fit
the requirements for a mathematical group.
For symmetry groups, closure means that any combination of operations
Once again, this is the same result as could have been achieved by a single u~ must be equivalent to an operation that is also a member of the group.
reflection. Since we reversed the order, this implies that combinations of C2 Inspection of the multiplication table for the operations of CBr2C12 shows
and Uv commute; that is, Cso; = uvC2 = u~ . In fact, all binary combinations that ali binary combinations equal either E, C2, UV, or u~.These four syrn-
of the four operations of CBr2Cl2 are commutative. You should verify that metry operations constitute the complete set of elements of a point group
the following results are correct: uvu~ = u~uv = C2 and C2U~ = U~C2 = Uv. called C2v' The multiplication table we developed in Section 1.3, then, is the
The results we have just obtained can be summarized conveniently in a multiplication table for the group C2v' The number of operations (group ele-
rnultiplication table, such as the following: ments) comprising the group defines the order oJ the group, designated h.
Thus, the order of the group C2v, is four (i.e., h = 4).
E C2 O'v 0" v

,
E E C2 O'v O'v Identity. In any group G, there is an element E (the identity element),
C2 C2 E O'~ O'v which commutes with any other element of the group, X, such that EX =
,
O'v O'v O'v E C2 XE = X. This requirement explains the need to define the symmetry opera-
O'~ O'~ O'v C2 E
tion of identity, which functions as the identity element for every symmetry
group. As the C2v multiplication table demonstrates, the identity operation
Although all combinations of the present four operations commute, in gen- does indeed meet the requirements for the identity elernent of a group.
eral this is not so, and it will be important to observe the order of combina-
tion. For multiplication tabIes of this type, the assumed order of combination
Associativity. The associative law of combination is valid for all combi-
is row element (top) first, followed by column element (side). In our right-to-
nations of elements of the group. Thus, if A, B, C, and X are members of the
left notation, the product BA = X would be re ad from a multiplication tabIe
group G and C(BA) = X, then (CB)A = X, too. When carrying out sequen-
as BcolumnArow == BsideAtop = X.
tial multiplications of operations, we may group the combinations into any
This multiplication table shows a number of features found in ali such ta-
convenient pairs, so long as the order of combination is preserved. We must
bIes. For example, the first row of results duplicates the list of operations in
preserve the order, because commutation is not generally valid; for example,
the header row, and the first column of results likewise duplicates the list of
it may be that CBA -=1= BAC.
operations in the label column. This must be so, because both involve com-
Using the C2v, multiplication table, we can demonstrate associativity for
binations with E. Also, note that every row shows every operation once and
any combination of three or more operations. For example, we can show that
only once, as does each column. Furthermore, the order of resultant opera-
C2( uvu~) = (C2Uv)U~. For the first combination we see
tions in every row is different from any other row. The same is true of every
column. Knowing these generaI features can greatly simplify constructing C2(UvU~) :' C2C2 = E
multiplication tables for other cases.
For the second combination we see

1.4 Symmetry Point Groups

Since both methods of association lead to the same result, they must be equal
The complete set of symmetry operations exhibited by any molecule defines to each other.
a symmetry point group. As such, the set must satisfy the four requirements We should note that, contrary to generally observed behavior, ali binary
of a mathematical group: closure, identity, associativity, and reciprocality. Let combinations of the group C2v do commute. A limited number of other
us examine these requirements, continuing with the example of CBr2CI2 and symmetry groups are similarly composed entirely of commuting operations.
the multiplication table we developed in Section 1.3 . In the mathematics of groups, any group in which ali combinations of

•
 20 Chapter 1 Fundamental Concepts 1.5 Point Groups or Molcculcs 21

elements commute is said to be Abelian. Therefore, the group C2v is an 1.5 Point Groups oJ Molecules
Abelian group.
The point group designations we have seen so far (C2v, C2, Cs, Cl) are exam-
Reciprocality. Every element A of the group G has an inverse, A -I, such ples of the Schonflies notation. This labeling system is used by most chemists
that AA -1 = A -lA = E. The meaning of the term "inverse" in this context is and spectroscopists, and therefore we will use it throughout this text. By con-
not the same as the familiar algebraic sense, where x and lIx are the inverses trast, crystallographers prefer the Hermann-Mauguin notation, which is bet-
of each other. In the theory of groups, two elements are the inverses of each ter suited for designating the 32 crystallographic point groups and the space
other simply because their binary combination commutes and is equivalent to groups used to describe crystal structures. Although we will not use
identity. Some elements may be their own inverses (i.e., A = A-I). We have Hermann-Mauguin notation, as examples of their form, here are the desig-
seen some examples of symmetry operations that are their own inverses; for nations that correspond to the Schonflies labels we have seen: C2v = mm,
example, C2C2 = E, 0-0- = E, ii = E, EE = E. Note that for the point group C, = m, C2 = 2, Cl = 1.
C2v every operation is its own inverse. Table 1.1 lists specific point groups and families of point groups that are
Among the operations that constitute a point group, there generally ex- important for c1assifying the symmetry of real molecules. As this shows, ali
ist smal!er sets that also obey the four requirements of a group. These smaller the chemically important point groups fall within one of four generai cate-
sets, which are groups in their own right, can be considered to be subgroups gories: nonrotational, single-axis rotational, dihedral, and cubico In the de-
of the larger group from which the elements were culled. In generai, if g is scriptions of families of groups among the single-axis and dihedral categories,
the order of a subgroup of a group whose order is h, then h/g = n, where n is n is the order of the principal axis, which can have a value from 2 to infinity,
an integer. In other words, the order of any subgroup must be an integer di-
visor of the order of the parent group. However, it is not a requirement that
subgroups for al! the allowed orders exist. Table 1.1 Common Point Groups and Their Principal Operations
For C2v, where h = 4, only subgroups with orders g = 1 and g = 2 are
possible. In this simple case, subgroups of both exist. From the multiplication Symbol Opcrations
table for C2v, we can identify the following subgroups, listed here with their
standard group notations and the elements comprising them: Nonrotational Groups
E (asymmetric)
Cl (E} E, UI!
C2 (E, C2} E,i
Cs (E, CTv}
Singlc-Axis Groups (n = 2, 3, ... , 00)
c, (E,o-:}
E, Ci; , C~-J
Since every value of h has 1 as an integer divisor and every group must con- E, Cn, , C~-I, no; (n/2 Uv and n/2 Ud if n even)
tain the identity element, the group Cl> which consists of E only, is necessar- E, Ci; , C~-l, 0-11
ily a subgroup of any other group. Indeed, it is the only possible group with E, S2n, ,S~::-l
order h = 1. A molecule that belongs to the group Cl has no symmetry (other E, C x, OOUv (noncentrosymmetric !inear)
than identity) and is therefore asymmetric. A molecule with only a C2 rota- Dihedral Groups (n = 2, 3, ... , 00)
tional axis belongs to the point group C2, and one with only a mirror pIane E, Cm , C~-t, nC2(l.C,,)
(CT) belongs to the point group C; In the list above, the group C, {E, CTv} and E, Cn, , C~-I, S2ro ... , S i;;-I, nC2(l. Cn), nUd

the group C, (E, CT~} differ only in the choice of which reflection piane of C2v E, Cm , C~-I, ';C2(l.C II),UI" no;
is taken to define them. Outside of that context, the point group Cs is defined E, Cco, S"', ooC2(l.C",), IJh, ooUv, i (centrosymmetric !inear)
as the set (E, CTh}, where the notation CTh simply indicates the single reflection Cubic Groups
piane of the group. E, 4C3, 4C~, 3C2, 3S4, 3SJ, 6Ud (tetrahedron)
Note that the sets (E, C2, CTv}, (E, C2, CT~}, or (E, CTv, CT~} are neither sub- E, 4C3, 4ci, 6C2, 3C4, 3C~, 3C2( = C~), i, 3S4, 3S~, 4S(;,
.. groups of Civ nor legitimate groups on their own. Aside from the fact that 4S~, 3Uh' 6Ud (octahedron)
these sets would have orders of g = 3 (not an integer divisor of the group or- E, 6C5, 6C~, 6C~, 6Ct, JOC3, lOC~, 15C2, i, 6S1O, 6SÌo,
der h = 4), they do not show c1osure. In each case, combinations among the 6S;0, 6S[0, lOS6, lOS~, 15u (icosahedron, dodecahedron)
nonidentity elements give elements outside the set.
22 Chapter 1 Fundamental Concepts 1.5 Point Groups or Molecules 23

depending on the specific group. As a practical matter, the value of n usually H F Br Cl

is not greater than 8 far any real molecule one is Iikely to encounter, with the
important exceptions of linear molecules far which n = 00. Examples of mel-
ecules belonging to various specific point groups in each family are shown in
"C/

Cl Br
r Cl
R Br
Fig. 1.14. Cl
The listings in Table 1.l for the single-axis and dihedral groups show se-
ries of rotational axes as C" ... , C~,-I. In keeping with the practice of indi-
cating operations as their simplest equivalents, some rotations in these series
may be represented more conventionally as equivalent lower-order rotations. ~l
The same is true for series of improper rotations, as in the farnilies of groups
Cl
S2n and DfI{J, where certain members are equivalent to lower-order proper ro-
tations (e.g., S~ = C4, S~ = C2, S~ = Cl). Furthermore, in the families of
groups Cnh and Dnh, which have both rotationai axes and a horizontai mirror
pIane (J,,) perpendicular to them, there are necessarily corresponding irn-
pro per axes. Some of the improper rotations, however, are equivalent to
other operations. As we have seen, SI = o; and S2 = i. Beyond these simple
equivaIences, some combinations of rotation with reflection give improper ro-
tations and others give lower-order proper rotations. The equivalences for a
series of C:,n operations (m = 1, 2, ... , n - l) combined with (Jh depends on
whether n and mare odd or even numbers. Specifically, if n is even, C;;'(Jh =
S:;'. If n is od d, C;:'(J" = S:;' when m is odd, and C;:'(Jh = sr= when m is
even. The details of these series, however, are not generally important for de-
termining the identity of a molecule's point group or for applying symmetry
arguments to chemical problems. Complete listings of operations for al! point
groups appear at the top of the standard character tables found in virtual!y
ali books on chemicaI applications of group theory (see Appendix A). It is
general!y more useful to understand the characteristic components that dis-
tinguish one family of groups from the others.

Nonrotational Groups. With their Iow orders (h = 1,2) and lack of an

axis of symmetry, the nonrotational groups represent the lowest symmetry
point groups. As previously noted, Cl is the point group of asymmetric rnol-
ecules, The group Cs describes the symmetry of bilateral objects that lack any
symmetry other than E and (J". The external morphoIogy of most mammals, F
for example, is nominalty bilateral, and therefore described by the point
group CS' The trisubstituted borane shown in Fig. 1.14 is a moiecuiar exarn- F ..",,, I ",.. F
F'" I
'''Co''''
pIe of Cs symmetry. The group Ci, whose onIy nonidentity operation is in-
version (i), is not a commonly encountered group, since most molecules that "'F
are centrosymmetric tend to have other symmetry, as well. The substituted F
cyclobutane species shown in Fig. 1.14 would have Ci symmetry. D3 Td Oh
Figure 1.14 Examples ofmolecules with various point group symmetries.
Single-Axis Rotational Groups. The sirnplest farnily of these groups is C II,

which consists of the operations generated by a C" rotation applied succes-

sively n times; that is, Cn, C,7, ... , C;,' = E. These groups are examples of an

•
 24 Chapter 1 Fundamental Concepts 1.5 Point Groups 01' Molecules 25

important type of groups, called cyclic groups. In general, a cyclic group of tations may be among the operations of the group. As the 2n notation im-
order h. is generated by taking a single element X through ali its powers up plies, only groups of this type with even-order principal improper axes exist.
to and including X" = E. Ali cyclic groups are Abelian, since ali their multi- The collection of operations generated by an odd-order S" axis is the same a
plications commute. Although some molecules belong to one of the Cn point that generated by the combination C" and Uh, which defines groups of the
groups (cf. Fig. 1.14), these groups are more frequently encountered because type Cnll' Examples of molecules belonging to any of the S211 groups are not
of their utility in simplifying problems of applied group theory. They often common. An example of a molecule that would belong to the group S4 is
provide a more compact working group to solve problems for molecules that shown in Fig. 1.14.
actually have significantly more symmetry than just the series of C" rotations.
Ali cyclic groups, including the C, groups, have rnultiplication tables with JJDihedral Groups. The dihedral groups have n twofold axes perpendicu-
a characteristic formo As an illustration, consider the multiplication table for Iar to the principal n-fold axis. These C2 axes are called the dihedral axes.
the point group C4, whose elements are the operations E, C4, cl = C2, cl. Every symmetry operation of a point group also acts on the symmetry ele-
ments of the other operations. Therefore, the number and arrangement of the
c4 E C4 C2 cl dihedral axes are dictated by the n-fold order of the principal axis. For ex-
E E C4 C2 cl arnple, suppose the principal axis of a dihedral group is C3. Then, once we de-
C4 C4 C2 cl E fine one perpendicular C2 axis, the operations C3 and C~ performed about
C2 C2 cl E C4 the principal axis will generate the other two C2 axes. Consistent with the C3
cl cl E C4 C2 angle of rotation, all three C2 axes will be arranged at 1200 from one another.
There are three families of dihedral groups: Dno DncJ, and DI/h' The DI!
The pattern of the products in each row, while unique, lists each element in groups may be thought of as Cn groups to which n dihedral C2 operations
the same sequential order as every other row. It is as if the elements were on have been added. Unlike the C; groups, the D'; groups are not cyclic. The
a continuous scroll, which moves one position to the left with each successive complex ion tris(ethylenediamine)cobalt (III), [Co(enh?+, in which bridging
row. This takes the first element of a row and makes it the last element of the ligands occupy cis-related positions about the octahedrally coordinated cobalt
next row. The columns seralI in a similar manner, moving elements up one ion, is an example of D3 symmetry (cf. Fig. 1.14).
and bumping the first element to the last position with each succeeding col- In the same manner, the Dnd groups afe related by dihedral axes to the
urnn. As a result, same elernents appear along right-to-left diagonals of the Cnv groups. In Dnd groups the combination of rotational operations and ver-
table. Knowing this pattern rnakes it very easy to construct the multiplication tical minor reflections (designated Ud in these groups) generates a series of
table for any cyclic group. S2n operations about an axis collinear with the principal axis. The staggered
To the rotations of the corresponding C; groups the family of C groups
IlV
conformation of ethane is an example of D3d symmetry (cf. Fig. 1.14).
adds n vertical mirror planes, which intersect at the C, axis. Molecular ex- The D"h family of groups bears the same kind of dihedral relationship to
amples of these groups abound. The point group C2v, to which CBr2CI2 be- the Cnh family. Like the corresponding single-axis groups, the Dnh groups in-
longs, is an example of this family. Other examples include NH3 (pyramidal, clude n-fold improper axes when n > 2 and are centrosymmetric when n is
C3v) and IFs (square pyramidal, C4v). (See Fig. 1.14.) The point group c.; even. Planar BCl3 and the eclipsed conformation of ethane are examples of
which has an infinite-fold C; principal axis, is an important member of this D3h symmetry. The group Dooh, in which the principal axis is an infinite-fold

family. It is the point group of alI noncentrosymmetric linear molecules (e.g., C"' is an important member of this family. It is the group of ali linear, cen-
HCI, CIBeF). trosymmetric molecules (e.g., H2, CO2).
To generate any of the C"h groups, we need only add a horizontal mirror The lowest members of the three dihedral families of groups, where
plane to the series of C; rotations of the appropriate cyclic C; group. However, n = 2, are in one respect unique. Tney ali have three mutually perpendicular
since CnUh = S" and C2Uh = S2 = i, these groups also have n-fold improper twofold axes, one of which is taken as the principal axis and hence the z axis
axes when n > 2, and they are centrosymmetric when n is even. A simple ex- of the reference Cartesian coordinate system. In older works, the D2 desig-
ampIe of this family is the C3h symmetry of trigonal planar borie acid, B(OHh, nation was given the special symbol V. Therefore, the groups D2, D2d> and
in which the B-O-H groups are presumed to be bent in the same direction D2h were formerly identified as V, Vd, and Vh, respectively. This notation is
(cf. Fig. 1.14). no longer used but maybe encountered when consulting older references, .'=-
The groups of the SZn family are generated from 212 successive 2n-fold im-
proper rotations about a single axis. The last operation in the series is equiv- Cubic Groups. The cubic groups are associated with polyhedra that are
alent to identity, si;. = E. Since S2 = i and S2n = Cm inversion and proper ro- geometrically related to the cube (cf. Fig. 1.15). Ali are characterized by the

•
 26 Chapter 1 Fundamental Concepts
r 1.5 Point Groups of Molecules 27

The octahedron and cube (Fig. 1.15) both belong to the point group Oh,
which is composed of the following 48 operatioos, grouped by cJass: E,
8C3(= 4C3, 4C~), 6C4(= 3C4, 3C~), 6C2, 3C2(= 3C~), i, 654(= 3S4, 3S1),
856( == 456, 45~),3a,,( = axy' ayZ' axz), 6aei. In the octahedron, a fourfold axis
emerges from each pair of opposite apices, whereas a threefold axis emerges \
Tetrahedron (Td) from e ach pair of opposite triangular faces. In the cube, a fourfold axis \
emerges from each pair of opposite faces, whereas a threefold axis emerges
fr orn each pair of opposi te corners, extending the diagonals of the cube.
Although molecules with cubic symmetry are rare, octahedral species are
common among six-coordinated transition metal complexes. A rarely en-
countered subgroup of O" is the rotational group O, whose operations are
simply the proper rotations that comprise Oh (see Appeodix A). Like the Tei
Octahedron (Oh)
rotational subgroup T, O is sometimes used as a simpler operating group for
problerns of molecules that actually have Oh symmetry.
Both the regular icosahedron and dodecahedron (Fig. 1.15) belong to the
poiot group h, composed of the following operations, listed by cJasses: E,
12Cs, 12C~, 20C3, 15C2, i, 12510, 12Sfo, 20S6, 15a. With h = 120, it is the high-
est symmetry that one is likely to encounter (aside from Cxv and D",}" for
which h == 00). In the icosahedron (Fig. 1.15) a fivefold axis emerges from each
Figure 1.15 Polyhedra belonging to the apex, while in the dodecahedron a fivefold axis emerges from the center of
Icosahedron (lh) Dodecahedron (lh) groups Td, Oh, and h. each face. The icosahedral ion B 12Hfi is an example of an Il! species. There
are currently no known examples of molecules with regular dodecahedral h
syrnmetry." However, buckrninsterfullerene, C6lh is an example of an even
presence of multiple, intersecting, high-order rotational axes. There are seven higher-order polyhedron with I; symmetry (Fig. 1.16). This soccer-ball-shaped
groups of this type, three of which are frequently encountered. These three carbon species consists of a spherical nel composed of five-membered rings
(Td, Oh, h) represent some of the most important geometries in chemistry. surrounded by six-membered rings. A fivefold rotational axis emerges from
The perfect tetrahedron defines the group Td, comprised of the following each pentagonal face, and a threefold axis emerges from each hexagonal face.
24 operations, Iisted by c1asses: E, 8C3 (= 4C3, 4C~), 3C2, 6S4 (= 3S4, 3SJ), Note that there are no sixfold axes, because each hexagon is surrounded al-
6ad· A threefold axis, generating the operations C3 and C~, emerges from ternately by three pentagons and three hexagons.
each of the four triangular faces of a tetrahedron (cf. Fig. 1.15). When a tetra- . As with the other cubic groups, Jh has a purely rotatiooal subgroup, des-
hedral molecule is inscribed in a cube, as in Fig. 1.10, a C2 axis collinear with ignated 1. The complete set of operations of this group is listed in Appendix
the bisector of opposing bond angles emerges from each pair of opposi te cube A. This is not an important group for considerations of molecular symmetry.
faces. Three S4 axes, each associated with S4 and S~ operations, are collinear
with these C2 axes. Any one of these can be taken as the z axis of a reference
Cartesian coordinate system. AIso, when the tetrahedron is shown inscribed
in a cube, each of the four C3 axes passes through a pair of opposi te corners
along a cube diagonal, collinear with an M-X bond (cf. Fig. 1.10). With
h = 24, Td represents one of the higher symmetries frequently encountered
in structural chemistry.
Two related cubic groups, T and Ti, also have four intersecting threefold
axes. The group T is a subgroup of Tei and consists of only the rotational op- Figure 1.16 Buckrninsterfullerene ("bucky ball"),
" erations of the higher symmetry group. Molecules with T and T» are virtually Coo, an example of h symmetry.
unknown. As we shall see later, the group T is sometimes used as a simpler
operating group to reduce the mathematical work of group theory applica- *Dodecahedral eight-coordinate (CN8) complexes, such as [Mo(CN)~]4- and [ZrF"l4-, actuaJly
tions for molecules that actually have Td symmetry. The complete sets of op- have D2d symmetry. [See J. L. Hoard and J. Y. Silverton, Inorg. Chem. 1963,2,235; and D. R.
erations for these groups may be found in Appendix A. Sears and J. H. Burns,1. Chem. Phys. 1964,41, 3478.]

•
28 Chapter 1 Fundamental Concepts 1.6 Systematic Point Group C1assification 29

1.6 Systematic Point Group Classification "Special Groups"

No Yes
Identifying the point group of a molecule is a necessary first step far almost
ali applications of group theory in chemistry. Given that the number of oper- C II

ations can be as high as 120 or even infinity, identifying a molecules point

No Yes
group by finding ali the symmetry operations is not a practical approach.
Fortunately, it is also not necessary. As we have seen, many operations are a" I I I
associated with a common symmetry element (e.g., C3 requires C~ about the No Yes C~v o.; Td O" I)
sa me axis); the presence of certain operations in combination requires the
i
presence of other operations (e.g., C3 and (J"h require S3); and each group can nC2's -L C II

be seen as a member of a family of groups with a characteristic set of sym- No Yes

metry elements (e.g., the dihedral groups ali have a single n-fold principal axis Cs
and n twofold axes perpendicular). The task, then, is reduced to finding the
essential symmetry elements of the molecule that c1assify its point group un- No Yes
equivocally. Cl Ci ah
ah
The best way to determine a molecule's point group is to look far key
symmetry elements in a prescribed sequence. Such a sequence is illustrated No Yes No Yes
by the "inverted tree" flow chart shown in Fig. 1.17. In using the flow chart, nav's na/s
look sequentiaIly for the symmetries indicated on the perpendicular lines, fol-
lowing the right or left branches according to whether a particular kind of No Yes No Yes
symmetry is present ("Yes") or absent (,'No"). S2n c; o.;
The sequence begins by determining if the molecule has one of the read-
No Yes
ily identifiable structures associated with certa in "special groups." These are
noncentrosymmetric linear C xv (e.g., HCI, FBeCl), centrosymmetric tinear c., Dn o.,
DXh (e.g., CO2, BeCI2), tetrahedral Td (e.g., CH4, SO~-), octahedral Oh (e.g.,
SF6, [Fe(CN)6]4-), and icosahedral or other polyhedral i, (e.g., B12H?i, C60).
Note that the geometry must be perfect for a molecule to belong to one of c; S2n
these groups. For example, while it is common in chemical discussions to re- Figure 1.17 Flow chart for systematically determining the point group of a molecule.
fer to the shapes of CH4, CH]Cl, CH2C!2, CHC!], and CC!4 as "tetrahedral,"
only CH4 and CCl4 have the complete set of symmetry operations that define planes) perpendicular to the axis of rotation. The number of equivalent atoms
Td. In this strict sense, the others are not truly tetrahedral. Both CH3Ct and Iying in any such piane will equal the order of the principal axis of rotation
CHCI] belong to the group C]v, and CH2CI2 belongs to the group C2v. (i.e., n value of Cn). If the molecule happens to belong to D2, D2d, or D2h, the
highest-order axes will be three mutually perpendicular twofold axes. In these
If it is apparent that the molecule is not one of these readily identifiable
cases, choose as the principal axis the C2 axis passing through the largest
structures, look for a principal axis of rotation. If there is no axis of rotation
number of atoms.
whatsoever, the molecule must belong to one of the low-symmetry nonrota-
Regardless of its order, once ayrincipal axis has been identified, deter-
tional groups-that is, Cs, Ci, or Cl. The specific group from among these can
mine whether the molecule belongs either to one of the dihedral groups (D
be determined by first looking far a mirror piane (often the piane of the mol-
groups) or to one of the single-axis rotational groups (C groups). To make the
ecule itself), which, if found, indicates C,.. If there is no mirror piane, look far
distinction, look for n twofold axes (dihedral axes) perpendicular to the prin-
inversion symmetry, which, if found, indicates Ci. The absence of both re-
cipal Cn axis (indicated as "nC2's ..LC on the flow chart, Fig. 1.17). These
Il"
flection and inversion indicates CI> the point group of an asymmetric species.
must lie in a common pIane, which may or may not be a minor plane of the
Often the molecule will have one or more rotational axes. If so, it is nec-
molecule. For example,' if the principal axis is C3, look for ,.three C2 axes at
essary to identify the highest-order rotational axis, the principaì axis, which
l20° to each other in a plane perpendicular to the C3 axis. The dihedral axes
will be taken as the z axis of the coordinate system (cf. Section 1.2). If a prin-
must intersect at the center of the molecule, but they are not required to pass
cipal axi exists, it will interrelate the greatest number of atoms or groups of
through any of the atoms (although they often do).
atoms, which will define one or more parallel planes (no t necessarily mirror
30 Chapter l Fundamental Concepts 1.6 Systematic Point Group Classification 31

If there are n twofold axes perpendicular to Cm then the molecule be- to a physical model as we search for the key symmetry elements. At the star t,
longs to one of the dihedral groups. To decide which one, begin by looking we recognize that PFs is a trigonal bipyramid, and therefore not a shape be-
for a horizontal mirror piane (Uh), which must contain the n twofold axes. If longing to one of the "special groups" (e.g., linear, tetrahedral, octahedral,
one is found, the molecule belongs to the Dnh group corresponding to the icosahedral). Therefore, we begin our systematic search for key symmetry el-
value of n for the principal axis. For example, if C3 is the principal axis, the ements by looking for a principal axis of rotation. Either from Fig. 1.18 or a
group is D3h' If no horizontal rnirror piane exists, look for n vertical mirror rnodel we may note that there are two symmetrically distinct kinds of bonds
planes intersecting at the principal axis (indicated as "nu,/s" on the flow in PFs· Two bonds (the axial positions) lie 1800 from each other and 900 from
chart, Fig. 1.17). If found, these minor planes indicate the Dnd group corre- the three other kinds of bonds (the equatorial positions). The three equator-
sponding to the value of n for the principal axis. It is crucial to look for a hor- ial bonds Iie 120 from each other within a pIane. We can define a rotational
0

izontal minor piane before looking for these Ud planes, because both Dnh and axis, collinear with the axial bonds, that relates the three equatorial bonds by
Dnd groups have vertical minor planes, which therefore provide no basis for the series of rotations C3, C~, and cj = E. By contrast, taking any one of the
distinction. If neither horizontal nor vertical minor planes are found, then by equatorial bonds as an axis relates only the two axial bonds by the series of
default the appropria te dihedral group is DI!' rotations C2 and C~ = E. Thus, the axial bonds lie along a C3 axis, and the
If the molecule has a principal axis but lacks n dihedral axes, it belongs equatorial bonds lie along C2 axes. There are no other axes of rotation, so the
to one of the single-axis groups. To distinguish between the possible groups, C3 is the highest-order rotational axis of the molecule, which identifies it as
begin as with the dihedral groups by looking for a horizontal mirror pIane the principal axis. We now know that PFs belongs to one of the rotational
(Uh)' If one is found, the molecule belongs to a Cnh group, where the value groups.
of n corresponds to the order of the principal axis. Thus, if the principal axis We next determine if the group is single-axis (a C group) or dihedral (a
is C3, the group is C3;,' If there is no horizontal minor piane, look for n ver- D group). To decide, we look for the three C2 axes perpendicular to the C3
tical mirror planes intersecting at the principal axis (indicated "nuv's" on the principal axis (nC2 ..LCn, where n = 3), the dihedral axes required of a D
flow chart, Fig. 1.17). If found, these mirror planes indicate the Cnv group ap- group. We have already noted that the three equatorial bonds lie along C2
propriate to the order of the C" principal axis. 1f there are no mirror planes, axes, so PFs must belong to one of the D groups (i.e., D3h, D3d, or D3).
the molecule belongs to a C" or S2n group. As a practical matter, it is more To decide among the possible D groups, we look for a horizontal mirror
likely to be the former than the latter. To decide, look for an improper axis piane (Uh), perpendicular to the C3 principal axis. The pIane of the three
S2n collinear with the principal Cn axis. With the possible exception of an in- equatorial bonds is a Uh piane. Its reflection operation interchanges the two
version center (e.g., if the group is S6), the Cn and S2n axes should be the only axial positions and reflects the three equatorial positions into themselves. At
symmetry elements (other than identity) if the molecule belongs to one of the this point we can conclude that the point group is D3h'
S2n groups. If the molecule lacks both mirror planes and an improper rota- In determining that PFs belongs to the point group D3h, we have ignored
tion axis, it belongs to one of the cyclic, purely rotational groups, Cn. some of the other symmetry elements of the group. The classification proce-
Among the single-axis groups, the Cnh groups are not frequently eri- dure only concentrates on finding the characteristic elements that uniquely
countered. As previously noted, borie acid is a simple example of C3h syrn- define a group. For example, we have not sought out the three vertical mir-
metry (cf. Fig. 1.14). By contrast, the Cnv groups are probably the most fre- ror planes (uv) that are among the elernents whose operations comprise the
quently encountered single-axis groups, and with practice they are among the D3h group. Each of the Uv planes passes through the two axial positions and
easiest to identify quickly. Both C; and S2n groups are so infrequently en- one of the equatorial positions of the trigonal bipyramid. The operation re-
countered among simple molecules that properly assigning a molecule that flects these three positions into thernselves, and it interchanges the other two
genuinely does belong to one of these groups can be tricky. As the S4 exam- equatorial positions, which lie on opposi te sides of the piane. These minor
pie in Fig. 1.14 suggests, molecules with S2ll symmetry tend to have somewhat planes are not unique to D3h' If we I1ad found these planes before finding the
exotic structures. As an operating principle, one is well advised to double Uh plane, we might have incorrectly assigned the point group as D3d, which

check that certain elements have not been missed when the procedure seems also has vertical minor planes. In other words, the order of carrying out the
to suggest one of these rare groups. A well-known medicai aphorism, offer- classification procedure is critical to a correct determination. We might also
ing sage advice to physicians attempting to reach a diagnosis from a set of
symptoms, is equally relevant to the process of determining a molecule's point F
group: "When you hear hoof beats, think horses, nOI zebras." F-~"'" F
As an illustration of the procedure, let us consider the systematic classi- I~F
fication of the point group of PFs (Fig. 1.18). You may find it helpful to refer F Figure 1.18 Trigonal bipyramidal structure of PFs.
32 Chapter 1 Fundamental Concepts 1.7 Optical Activity and Symmetry 33

note that D3h has an S3 axis collinear with the C3 axis. This must be so, be- group is D3 (cf. Fig. 1.19)* We can generalize these relationships for any mol-
cause both C3 and (Th exist, and (ThC3 = S3 by definition. Our classification ecule that can be represented as two regular polygons separated along a prin-
procedure does not require finding the S) axis, since the point group in this cipal axis of rotation. When the polygons are eclipsed, the group is Dnh; when
case is determined by the presences of other necessary elements. they are perfectly staggered, it is Dnd; and when they are skewed, it is Ir.; As
Grouped by classes, the complete set of symmetry operations that com- a test of this, you might want to make a model of ferrocene, Fe(CsHsh, and
prise the point group D3h is E, 2C3 (= C3, cj), 3C2, (Th, 2S) (= S3, S~), 3 (Tv. systematically determine the point groups of the configurations resulting
There are 12 operations in this list, so the group order is h = 12. The 12 op- from the three types of ring alignment.
erations are associated with lO symmetry elernents: the object itself for E; the
C3 proper axis for the C) and C~ rotations; the three dihedral C2 axes, one
for each C2 rotation; the horizontal mirror pIane for the (T" reflection; the S3 1.7 Optical Activity and Symmetry
improper axis (collinear with the C3 axis) for the S3 and sj operations; and
the three vertical mirror planes for the three (Tv reflections. Many molecules can exist in either of two optically active isomers, called
The flow chart of Fig. 1.17 is a convenient mnemonic for learning sys- enantiomers. When plane-polarized light is passed through separate samples
tema tic point group classification. However, with practice, reference to the of enantiorners, one (the dextrorotatory isomer) will cause clockwise rotation
chart should become unnecessary. * Indeed, chemists experienced in symme- of the polarity, and the other (the levorotatory isomer) wil! cause counter-
try classification often can determine the point groupof a rnolecule'almost in- clockwise rotation of the polarity. Compounds that can exist as enantiomeric
stantly, even without needing to carry out a sequential arralysis. In part, this pairs are called chiral; and from the standpoint of symmetry considerations,
is possible because certain structure patterns reèur frequently and become as- they afe said to be dissymmetric. Dissymmetric is not the same as asyrnmet-
sociated in the mind with their appropriate point groups. ric (despite what some dictionaries may suggest). Asymmetric means the ab-
The three conformations of ethane exemplify one type of recurring geo- sence of any symmetry other than identity. In contrast, dissymmetric mole-
metrica] pattern. To see the pattern, imagine the two sets of three hydrogen cules may have significant, albeit limited, symmetry. Asymmetric molecules
atoms on each end of ethane as two triangles separated by a distance (cf. Fig. are simply the least symmetric of dissymmetric molecules.
1.19). Looking down the principal axis (C3), we find that the point group is The hallmark of enantiomers is that they are nonsuperimposable mirror
D3h when the triangles are aligned (eclipsed) and D3d when they are perfectly images of each other. Figure 1.20 shows two examples of such dissymmetric
staggered. We note further that if the triangles are slightly misaligned (skewed enantiomer pairs. As expected, asymmetric CHBrC1F has two nonsuperim-
configuration), the vertical rnirror piane symmetry is destroyed and the point posable isomers and therefore is chiral. However, the complex ion [Co(en)3]3+
also exists as two enantiomers but has significant symmetry, belonging to

H
I
C
s.:..'"~""""F
CI
r.1.
-, n
J)l .
r.
.:--:.-- ./

,-/~l'-v

( .."",,,I~
Co . Figure 1.20 Enantiomers 01 dissym-

Figure 1.19 Representations of the three confor- ~I~ metric species. CHFCIBr (point
group Cl) is asymmetric, but
mations of ethane as two triangles separated along [Co(enhJ3+ (point group D3) is not.
the C3 axis. The corresponding Newrnan projec-
tions are shown on the right. *You may want lo build models of aH three conformers to verify these point group assignments.
The dihedral axes can be difficult to see for the staggered and skewed configurations. Looking
*To help develop your facility with systematic c1assification, you rnight try verifying the point at the Newman projections (cf. Fig. 1.19), you can find the C2 axes as bisectors or the angles be-
group assignments given for the molecules shown in Fig. 1.14. lween pairs of C-H bonds on the "front" and "back" or the projection.
34 Chapter l Fundarnental Concepts Problerns 35

,
Il (fr\(~ /fi4JeccfÒ-l'w ,0, j:':-u.. 1.4 Cyclic groups are formed by taking the series of powers on a single element up
I
c);/ll.J-t t1J. i u_/):(I'f1!);,_{)r' (,j, éJ to the order of the group, such that G = [X, X2, ... , Xh = E]. Taking each of the

120(J_ I -,:
I
H -
oQL'tl- following operations as the base elernent of a cyclic group, determine the series
I

1;( fr-G'>- ~l~_ i)~{~'{IfV,d.t,-.~,

'BHfl!. k Tw-L19A..,;. éf--.

of all operations that constitutes the group, identify the group, and develop its

",/ --a1-:J::;°- __-,_,-//

r:rJ. -ff-L.~yt~' multiplicationtable: (a) C3, (b) C6, (c) 54 Identify all the subgroups of these
cyclic groups.
H ' Figure 1.21 The structure of hydrogen per- 1.5 Develop the multiplication table for the group C2h, which consists of the opera-
tions E, C2, i, and a.; [Hinl: Determine the effects of the operations on an arbi-
oxide (point group C2).
trary point whose initial coordinates are x, y, el Is this group Abelian?

point group D3. As this illustrates, chiral molecules may have some symme-· 1.6 Determine the point group of each of the following shapes:

t!t
try, In generai, the restriction is that a molecule is dissymmetric and may be J
chiral either if il is asymmetric or if has no other symmetry than proper re:
ù

tation. The point group D3 satisfies the latter criterion, since the group con-
(a) Q (c)

*
sists of the operations E, 2C3, 3C2. In light of these restrictions, only mole-
cules belonging to certain point groups are candidates for chirality. The
possible chiral groups are Cl (asymmetric), Cn, and Dn*
(d)
(e) <§l (f) >-
The traditional test of chirality is to draw or build models of the suspect
species to see if nonsuperimposable, mirror-irnage isomers exist. As a practi-
cal matter, this exercise need only be carried out if the molecule belongs to
one of the possibly chiral point groups. In most cases, molecules belonging to
any of these groups will be chiral, but in rare cases enantiomeric pairs cannot
(g) ~ (h) T
actually exist. For example, hydrogen peroxide, B202, whose structure is
(j) a Styrofoam coffee cup (no decoration)
shown in Fig. 1.21, belongs to the point group C2 but is not optically active. (k) a ceramic coffee mug with handle (no decoration)
While it is possible to build two models that are not superimposable, the dis- (I) a dumbbell (no markings)
tinction does not exist for the actual molecular structure, because relatively (m) a tennis ball, including the seams (o ne colar, no markings)
free rotation about the O-O bond continuously interconverts the two hypo- (n) an airplane propeller with four blades
thetical enantiorners. Bere, stereochemical nonrigidity precludes chir ality, (o) a soccer ball, including the seams (one color, no markings)
1.7 Determine the point group of each of the following molecules or ions, whose
shapes can be determined by use of valence-shell electron-pair repulsion
Problems (VSEPR) theory: (a) SeF s,
(b) CIFr, (c) AsF4, (d) XeF2, (e) XeF4, (f) BeF},
(g) SiFl-, (h) OCW, (i) AsCl~, (j) OSF4, (k) trans-FNNF, (1) cis-FNNF, (m)
1.1 For the following molecules, which afe shown in Fig. 1.14, sketch the locations ClSSCl (nonplanar), (n) S20~-, (o) trans-(OH)4Xe02·
of all the symmetry elements, and Iist al! operations associated with each sym- 1.8 Consider the following ideaI geometries far MX" molecules (n = 3-6) and the
metry element: (a) NH3 (C3v), (b) IFs (C4v), (c) B(OH)3 (C3,,), (d) BCl3 (D3,,), distortions described far each. What are the point groups of the ideai geometry
(e) C2H6 in the staggered conformation (D)d). and the distorted geometry?
1.2 Given the set of operations (E, C4, (ThL determine the other operations that must (a) MX) trigonal planar distorted by lifting the M atom out of the plane.
be present to form a complete point group. [Hint: Consider all the products of (b) MX4 tetrahedral distorted by-slightly flattening the rnolecule along one of
the given elements with themselves and with each other.] Identify the point ~~~. .
group for the complete set of operations, What is the order of the group? (c) MX4 square planar distorted by equally elongating two trans-related M-X
1.3 Aside from the trivial group CI, the point group formed from the complete set bonds.
of operations from Problem 1.2 has six subgroups, Identify the subgroups and (d) MXs trigonal bipyramidal distorted by equally elongating or shortening the
give the order of each. two axial bonds.
(e) MX, trigonal bipyramidal distorted by elongating one of the equatorial
bonds.
*The rotational cubic groups T, O, and [ can also be added to this list, but no molecules with (f) MXs trigonal bipyramidal distorted by elongating one of the equatorial bonds
these symmetries are likely to be encountered. and shortening one of the axial bonds (or vice versa).
 36 Chapter J Fundarnental Concepts Problerns 37

Qlnl~~
(g) MX6 octahedral distorted by elongating two trans-related bonds.
(h) MX6 octahedral distorted by slightly closing the 90° angles between the three
M-X bonds in both sets of cis-related positions.
1.9 Identify the point group for each of the following FeJ+ complexes with the biden-
tate oxalate ligand (ox = C20~-). Where allowed by the point group, determine
which complexes are chiral. [Hint: Use models to help identify the point group
WC1 ~ F F F F
and to verify the existence of enantiomers.]
(q) (r) (s) (l)
(a) tris( oxalato )ferrate(III), [Fe( oxhf-
(b) lrans-dichlorobis( oxalato )ferrate(III), [FeCl2( ox)z]3-
(c) cis-dichlorobis( oxalato )ferrate(III), [FeCI2( OX)z]3-
x x
(d) cis-di bromo-trans-dichlorooxalatoferrate(III), [FeBr2Cl20x]3-
(e) cis-dibromodichlorooxalatoferrate(III), [FeBr2CI20x f-.
1.10 Identify the point group of each of the following structures.

LL F~~
Cl Cl
F~
CI F Cl
Fl(CI F (u)
X
( v) (w)
(a) (b) (c) (d)

o CI-Q
Cl

~ ~ ~
F
F~
F ClD
O OCi OCi
F F F CI F F F F F Cr _
Cr
(e) (f) (g) (h)

F F

p:j
c:::J
••
Cl
FPCl (x) (y) (z)
F F CI CI
(i) (j) (k) (l)
1.11 Identify the point group of each of the following cyclopentane derivati ves in the
configurations shown.

8 HA~
F

~F~
~ ~ ~
F
F F
(m) (a) (b) (c)
(n) (o) (p)
 38 Chapter 1 Fundamental Concepts Problerns 39

00 V b
F F F

~ ~ ~
À (k) (l)
F (i) (j)

(d) (e) (I)

F
tb 1; ~ À
F (o) (p)
Cm) (n)
F

?b C2J
F

(g)

F
(h) (i)

F
~ #
CC?
(r) (s) (t)
(q)

~
F
(j) (k) (1)

1.12 Identify the point group of each of the following structures.

(a) (b) (c) (d)

(e) (f) (g) (h)