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Molecular Symmetry 2

Molecular Symmetry 2

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Published by Kirk Borromeo

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Published by: Kirk Borromeo on Feb 13, 2010
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30
 Dry Lab III: Molecular SymmetryChemistry 373
7. Dry Lab III: Molecular Symmetry
Topics:1. Motivation2. Symmetry Elements and Operations3. Symmetry Groups4. Physical Implications of Symmetry1. MotivationFinite symmetries are useful in the study of molecules. They are used in the classification of molecules, simplifying quantum mechanicalcalculations on molecules, determining the presence of certain molecular properties such asmolecular polarity and chirality. In the next twodry labs, we will focus on finite symmetries andgroups of finite symmetry operators.We will use P.W. Atkins,
 Physical Chemistry
, Chapter 15, as our principlereference. Another book by F.A. Cotton,entitled
Chemical 
 
 Applications
 
of 
 
GroupTheory
, either the first or second edition, is anexcellent source book too.In Chemistry 331/333, you have had someexposure to finding symmetry elements andsymmetry operations. This Dry Lab is meant to be a either a practical review or an introductionto symmetry elements and symmetry operations.The set of all symmetry operations for amolecule form a mathematical structure called agroup. Here, we will look at group structure,classes of symmetry operations, and the namingof molecular point groups. We will examinehow to use the group structure to predict when amolecule is polar or chiral. You will apply theseideas to several molecules or molecular ions.2. Symmetry elements and operationsA symmetry operation will transform a moleculeinto itself so that the transformed molecule will be indistinguishable from the original structure.Also, at least one point in the molecule will beleft undisturbed by the transformation. Hencethe origin of the name molecular 
 point 
group.Often, two or more atoms are permuted duringthe course of the molecular transformation.Since atoms of the same type areindistinguishable, the transformed molecule isindistinguishable from the starting molecule.So, a molecular point group consists of all thosesymmetry operations that leave a point in themolecule invariant and permutes identicalatoms.
1
Symmetry operations come in severalflavours: inversion, reflections, rotations, andimproper rotations, and of course no operation atall. The last operation is called the
 
identity
 
operation and is present in all molecules. It isnormally denoted by the symbol E. For eachsymmetry operation there corresponds asymmetry element. More than one operationmay correspond to the same symmetry elementA rotation operation takes place about arotation axis. A rotation takes place through anangle of 2
π
/
n
. (By convention, a rotation by a positive angle is considered to becounterclockwise, a rotation through a negativeangle would then be clockwise.) Such a rotationis said to be an
n
-fold rotation. The rotation isabout some axis in the molecule called an
n
-foldrotation axis. If a molecule has more than onerotation axis, the one with the highest value of 
n
is called the principal axis of rotation.
2
The
n
-fold rotation operation is denoted by C
n
(plaintext) and the axis of rotation is identified by thesymbol
n
 
(italics). For example, the water molecule has one principle axis of rotation, a 2-fold axis,
2
, through the O atom and bisectingthe HOH angle. This a rotation by 180
°
,transforming the molecule into itself. Incontrast, the BrF
5
molecule has a 4-fold axis,
4
,of rotation containing the axial BrF bond. Notice that a 4-fold axis always contains a 2-foldaxis. For example, the square planar structureXeF
4
has a
4
axis through the Xe atom andorthogonal to the plane of the molecule.Carrying out two consecutive 4-fold rotations,i.e. C
42
= C
4
C
4
, about a
4
axis is equivalent toconducting a C
2
rotation about the same axis.Therefore, the
2
axis is coincident with the
4
axis. In H
2
O, the
2
axis is the principal axis of rotation. In XeF
4
, the
4
axis is the principalaxis of rotation. For a diatomic molecule, arotation by any arbitrary angle can be performedabout the internuclear axis. Such an axis iscalled a
×
axis and is the principal axis of rotation. 
1
Note that not all identical atoms need be permuted amongst each other. We shall see anexample of this later.
2
The principal axis of rotation need not beunique.
 
31
Chemistry 373Dry Lab III: Molecular Symmetry
A reflection takes place in a plane of symmetry , sometimes called a mirror 
 
 plane . Thereflection operation is denoted by
σ
(plain) andthe mirror plane are both denoted by
σ 
 
(italics). Normally, reflection planes contain rotation axesor are orthogonal to an axis of rotation. If a plane is orthogonal to a principal axis of rotationit is designated by the symbol
σ 
h
. If a planecontains a principal axis of rotation it is usuallydenoted by
σ 
v
. If the plane bisects the angle between two C
2
axes it is called a
σ 
and such a plane is called a dihedral plane of symmetry.
3
Often, other criteria are needed to distinguish between
σ 
v
planes and
σ 
planes. Water has tworeflection planes, both of them
σ
v
planes. InXeF
4
, the reflection plane orthogonal to the
4
axis (the principal axis) is a
σ 
h
plane.An inversion operation, I (sometimes writtenas i)
 
, through the centre of inversion (
 I 
or 
i
)takes the point (
 x
,
 y
,
 z 
) in the molecule andtransforms it to (-
 x
,-
 y
,-
 z 
). The chemicalenvironment at the points (
 x
,
 y
,
 z 
) and (
 x
,-
 y
,-
 z 
) areidentical. Water does not possess an inversioncentre whereas XeF
4
does.An
n
-fold improper rotation,
n
, about an
n
-fold improper rotation axis (same symbol) iscomposed of two successive transformations:The first component is an
n
-fold rotation about
n
followed by the second component, areflection in a plane orthogonal to the
n
axis. Note that the
n
-fold rotation need not correspondto an actual
n
-fold rotation axis in the molecule.Similarly, the reflection plane orthogonal to the
n
axis need not be an actual reflection plane.The water molecule does not possess animproper axis of rotation. A CH
4
molecule hasthree
4
axes but no
4
axis.3. Symmetry GroupsWe use the phrases symmetry groups andmolecular point groups synonymously.A mathematical group,
G
= {
G
,
}, consistsof a set of elements
4
 
G
= {E, A,B,C,D,....} anda binary relation, called group multiplication or  
3
Frequently, the
σ 
h
plane is called a horizontal plane and the
σ 
v
plane is referred to as a verticalreflection plane. There is some danger in doingthis since not all
σ 
h
planes need be “horizontal”and not all
σ 
v
planes need be “vertical.”
4
Do not confuse symmetry elements discussedin section 2 with group elements. The set of symmetry elements do not form a group, onlythe symmetry operations form a group. Theterm element used in this definition is standardusage in set theory.group product or simply multiplication or  product, denoted by ‘
’, which satisfies thefollowing properties:(a) The product of any two elements A and B inthe group is another element in the group, i.e.,we write A
B
 
G
.(b) If A, B, C are any three elements in thegroup then (A
B)
C = A
(B
C). Therefore,group multiplication is associative, andfrequently, we omit the brackets.(c) There is a unique element E in
G
such thatE
A=A
E=A, for every element A in
G
. Theelement E is called the identity element.(d) For every element A in
G
, there is a uniqueelement X in
G
, such that X
A = A
X = E. Theelement X is referred to as the inverse of A andis denoted A
-1
. The identity is its own inverse.The number of elements in a group is calledthe order of the group. Frequently, it is denoted by the symbol
h
.Frequently, when no confusion can arise thesymbol ‘
’ for the product is omitted. Also,when there can be no confusion, we will use thesymbol G for the group rather than
G
.If we think of the group elements assymmetry operations of a molecule and if byA
B we mean “first we perform the symmetryoperation B on the molecule followed bysymmetry operation A.” The net result of suchconsecutive action on a molecule is another symmetry operation. Take dichloromethane asour example. The molecular structure andCartesian axis system are shown below.
xyz
ClClCH
A BAB
H
 
32
 Dry Lab III: Molecular SymmetryChemistry 373
Think of the Cartesian axes as being centred atthe C atom with the z-axis bisecting the HCHand the ClCCl angles. The x-axis lies in theHCH plane, while the y-axis is in the ClCCl plane.The identity operation,
 E 
, leaves the moleculeunchanged. The
2
axis lies along the z-axis.The C
2
operation transforms the dichloromethanemolecule as
A BABAA
HCCl ClHH
2
CllHC
Carrying out two consecutive C
2
operations isequivalent to the identity transformation. Thereare two reflection planes in the molecule; bothcontain the rotation axes. One plane is the planeof the page; containing the ClCCl plane. Wedenote this plane by
σ
(yz). The second plane is perpendicular to the plane of the page; denote it by
σ
(xz). The action of 
σ
(yz) is to give thearrangement of atoms shown below, where thetwo hydrogen atoms have been interchanged,while the two chlorine atoms and carbon are
CClCl
A BA
HHCClCl
A
HH
σ
(yz)
unchanged. The
σ
(xz) permutes the chlorineatoms but leaves carbon and the two hydrogenatoms fixed. This is represented in thefollowing diagram
A BABA
CCllHHCClClHH
σ
(xz)
Applying the plane
σ
(yz) twice, i.e., (
σ
(yz))
2
=
σ
(yz)
σ
(yz) = E, we get the identity. This meansthat
σ
(yz) is its own inverse. Similarly, we findthat (
σ
(xz))
2
=
σ
(xz)
σ
(xz) = E, and
σ
(xz) is itsown inverse. Now, if we carry out a
σ
(xz)reflection first and follow it by a
σ
(yz) reflection,we get
A BABA
CCllHHCClClHH
A
σ
(yz)
σ(
xz)
Comparing this diagram to that of a C
2
rotationwe see that the result is identical. Therefore, wesay that
σ
(yz)
σ
(xz) = C
2
(1)You can show that performing the reflections inreverse order yields the same result. Note thatthe symmetry elements remain fixed and are nottransformed to new positions when the atoms inthe molecule are moved to new positions. Whatabout carrying out a C
2
rotation followed by thereflection
σ
(yz)? Performing these symmetryoperations yields
CClCl
A BAB
ClCl
A
HH
σ
(yz)C
2
HCH
which is equivalent to a
σ
(xz) operation. Showthat carrying out these operations in reverse order affords the same result. Next, we compute the product
σ
(xz)C
2
:
A BABBBAA
HH
σ
(xz)C
2
HCHCClClClCl
and this is identical with a
σ
(yz) operation.Again check that the reverse sequence of operations yields the same result.Using the definition of the group and the products of symmetry operations that we have just uncovered, we can construct a
 
group
 
multiplication table :
C
2v
EC
2
σ
(xz)
σ
(yz)EEC
2
σ
(xz)
σ
(yz)C
2
C
2
E
σ
(yz)
σ
(xz)
σ
(xz)
σ
(xz)
σ
(yz)EC
2
σ
(yz)
σ
(yz)
σ
(xz)C
2
EThis table contains all the information about thegroup and its structure. The name of thismolecular point group is C
2v
. There are someobservations to make about this table.(1) Notice the inner four-by-four box. In eachrow and each column, each operation appearsonce and only once. In other words, each rowand each column is a permutation of the others.This is a feature possessed by all groupmultiplication tables.(2) We can identify smaller groups within thelarger one. For example, {E,C
2
} is a group.There are two others; what are they? Thesesmaller groups are called subgroups of C
2v
.

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