What use is group theory?

Thereis no doubtthat grouptheoryis of pivotal importance chemistry.In most undergraduate in chemistry courses, grouptheorycourse the comes abouthalfwaythrough wholeof the chemistry the course.By this time the basicconcepts usedin chemistry will havebeencovered-especially ideasof atomicorbitals, the bonding molecular theories, vibrations, molecular configurations. take theseideasfurtherit To shapeand electronic necessary understand becomes to something aboutgrouptheory. Indeed, courses which follow the grouptheory (andterminology) quiteextensively. course likely to build on theconcepts are ofgrouptheory Unfortunately, is true that somestudents find their first encounter it can with grouptheoryan uncomfortable one. In manycases canbe traced this back to a lack of familiaritywith the mathematical concepts group that theoryuses,and in othercases is relatedto the difficulty in 'seeing'the symmetryoperations it involvedin examining molecule's a overallsymmetry.Evenfor the students arefamiliarwith themathematics can who and perform three-dimensional manipulations theirhead in with little difficulty,thewholereason grouptheory for can be unclear. your starting point whenit comes understanding Whatever grouptheory,it is important to that you can at leastusegrouptheoryto solvesomechemical problems, thatyou arefamiliarwith the terminology, and which popsup again agarn otherareas chemistry. and in Hopefully bookcanhelpanychemistry of this student studying grouptheoryfor the first time. If you areonewho findsgrouptheoryunpalatable because the mathematics, of thenyou should knowthatusinggroup in theory chemistry onlyrequires simple arithmetic: more! (Of course, no a fullerunderstanding grouptheory of requires mathematics.) fact,theexercises thisbookcanbe completed In in withouthavingto readthe'mathematical'bit (Section at all. If you areoneof thosewho findsit difflcult to 4) 'see'thesymmetry properties a molecule, of perfect'. The workedexercises thenrealise that 'practice makes in this book aredesigned exactlyfor this pufpose, makeyou moreconfident handlingthe three-dimensional to in shape molecules. of And, finally,if you areonewho just cannot wheregrouptheoryhts in andwhereit all see leads, Lhen someof thesimpleexplanations thisbook-particularlythose Section in in S-will hopefully helpto makethingsclearer. Certainly,doing the workedexercises help you to seethe use of group theoryin will chemisUy. This book is meantto be writtenin. Doing the exercises an important is part of completing book,and the for to 1'oushouldhavea pencilat hand. Thereare spaces you to write yoru answers the problems.The full answers ihengivenimmediately are below. Try to resistthetemptation look at the answer to beforeyou attempt it theproblem; mighthelpto cover'up answer the with a pieceof paper.In saying this,do not expect getevery to arswercompletely right first time,it wouldbe remarkable you did. It will alsobe very usefulto havea small if molecular modellingkit nearby(some'Blu-Tack' and strawsare a usefulsubstitute you do not possess if a molecular modelling kit). Of course, somesections takelongerto complete will thanothers, it is probably but realistic try ard complete to eachsection onesitting.Try to understand ideas in the covered each in section before proceedilgto the next one,and watchout for the terminology, which will keeppoppingup. By the endyou will havecovered nearlyall of theusesof grouptheoryin chemistry, a f,irstlevel of understalding.This shouldbe to enoughat leastto use group theoryto solveproblemsthat you are likely to encounter chemistry, should in but alsoprovidea firm foundation ifyou areinterested takinggroupttreoryfurther. in

SECTION 2

Symmetry-a start

r -n l S t r ] - ' . : \l l m e
- nrlinr' -::her lt . :heory : :-table r. !rOUp led in :llrl Can :\' can - -.in at .'.hich . .1 \'1ng
:l..rllCS,

2.1 2.2 2.3 2 .4 Z ,5 2.6 2.7 2.8

An introduction to symmetry Rotation axes Reflection planes Centres of inversion Improper rotation axes Successiveoperations, identity, inverse and class Point groups Summ4ry

4 4 7 13 18 )< 29 33

: . . ' i ee d t -. iltt0
- .is ill ' .:,jllal

:, :l all I .:rirtO , :r' in .. .ud - iull : .-ll1pt J\.ery ..nrall : 'i\S a

-.rblY

-- iorc . ri'ill . . Jb e . . ., u l d

Symmetry-a

start

2.1

to An introduction symmetry

object over an From an early agewe have an understandingof symmetry. It is easy to spot a symmetrical into chemistry. For instance,it is easy to say which unsymmetricalobject. These qualitativeideas also extend 'symmetrical'. of the moleculesbelow is the most

OH

cl

,symmetrical' molecule is benzene. Why is it important to know this in chemistry? To answerthis, The most 1H-Mr4R spectraof the two molecules. Despite the close structuralsimilarity of the one has only to look at the for 2-chlorophenol two molecules, the spectrum for benzenecontains a single peak, whereas the spectrum pattern. Clearly then, even at a qualitative level, containsseveralpeaks split by a complicatedcoupling 'hand-waving' make some symmetry has something to Oo with the energy levels of a molecule. We can here that all oittre benzenehydrogen atoms are in the same chemical environment, but it is difficult to ,gu-"ni, is important in go"mucn further, and it is impossible to say anything more quantitative about how symmetry Therefore,if we are ever to say anything quantitative about the determiningthe energy levels of a molecule. powerful in predicting energy levels and symmetry of a molecule-and clearly, this may prove to be extremely to define the symmetry of a molecule. Indeed,this is ,p..t.u of molecules-we must provide some type of rules 'symmetry' of a the the subiect of this section: putting what we already do well qualitatively in determining applied to any finite molecule on to a more quantitativebasis. The symmetry rules we shall consider can be in the context of the shapeof molecules' object,but we shall only considerthe rules

2.2

axes Rotation

rotation. For example,look The first type of symmetry which we will examine is symmetricalbehaviourupon 'Vfigure on the next page. The molecule has the well-known at the structure of the water molecule in the plane of the paper. We can shape', and for our purposesimagine that the molecule is contained within the oxygen atom and bisects the H-O-H angle, all in the plane of the imagine an axis, wfrich passesthrough the which is pup"r. If the molecul; is rotated by 180'about this axis, then we end up with the molecule 'indistinguishable words, the water molecule is symmetric to rotation by 180" about from the original. In other it is indistinguishable. this axis. (The molecule after iotation is not identical n rhe molecule before rotation, but upon rotation. Of course,the H1 and H2 Ne interchanged If the hydrogenatomsare given imaginarylabels,then axis can be defined hydrogenuto1n.." the samein the real molecule.) Such symmetricalbehaviour about an is symmetric by rotation of -r degreesabout an axis' then we more mathematicallyas follows. If the molecule (360/180) = 2. Therefore,this is a have a rotation axis of order (360/-r). So, for water, the order of the axis is name C2. secondorder axis, which is given the shorthand

Symmetry- a start

Rotateby 180"

--9---*, H;
i
Somenotesof terminology. .

--,.>

*(o\r,

The axis is known as the symmctm elemcnt.

.
a: an
i:-,1Ch

Theactual transformation themolecule its symmetrical position knownastbesymmetry of to equivalent is operation. is Therotation clockwrse.

the So,for thewatermolecule, C2 axisis thesymmetry element, whereas rotation 180"aboutthis axisis the of operation. rhesymmetry

Now, sketchwhat happensto the water molecule(labelling the hydrogenatoms2s above),when the C2 is operation carriedout on it twice in succession.

,r1s, : rhe
:: llOl -. rl ' ,,5

-.:t0 :.: ln : t:he , ind - .\: i S ta trrte

Answer

c2

-+

*{o\r,
. rok Jan : rhe -. 15 trul - :he ::ed :we \a

,(o\*,
c2 --_+

,{o\*,
l:.e successive applicationof two C2 operations the water molecule,gives back the original molecule,which on ; :dentical to the molecule that we startedwith. Overall, nothing has happenedto the molecule. In fact, the

grouptheory chemistry for Beginning

doingnothtn3 aboveshows, onein grouptheory. As the example by of doingnothingis an important molecule 360" abcu: operation oplruilont'ot asthe rotationof the asrhe multiple application ,y;;;; Sucha symmetn canbe seen in 'doingnothing'i. t symmetry "f operation its own right' in thener' will an axis(a Ct axis)unO'tr,L"ro., a'do nothing'operation be seen of iraving uy is denoted thetetterE. The impoit'aoce operation

or c': operation seciion a c2^a1isl: 91111'T^-{:t""li3:5i'}:':"T;11to E' In fact' thc bv operationr80"about rotation tn^t c22 is equivalent
the symbol 7?. t Ju" utr^"^.::.:::: followed by anorher c2r is given to E' n is a positive-integer)is equivalent seneral case of cnu (where irathematicallY as follows:

This can be expressedmore

Czl.Czl=Cz2=E Crn or, moregenerallY = E

(axes)' and axis(axes) theorderof theaxis and molecule work outif-it hasa rotation the Sketch ammonia of themolecule' ni.*-itt" t-ls (axes)on yorrrsketch

T h e m o l e c u l e p o s s e s s e s a s i n g l e r o t a t i . o n a x i s o fformed3 . T thea x i s phydrogenratoms't h e n i t r o g e n a t o m a n d o r d e r by h e three a s s e s * t o u g h fiiangle rhrough rhe centre or.o'lirug^i"n}v "quiiu*.ur

LI

Caaxis

.,,'ivt
H

What about molecules only possesses onerotationaxis of symmetry' molecule the Clearly, ammonia axis morethanonerotational of symmetry? whichpossess

be Figureout all of the rotationaxesthat can the the nexrpagesketch ,t u"tor" ITI6E*. pictureof on thetop of the nere),andsketch axeson your modelkit -uv t" (a foundfor benzene molecular "."ru

Symmetry-a slart

Answer

c6 c3 c2

c2'

92"

containsa surprisinglylarge numberof rotation axesof symmetry,which are shown in the figure above. Benzenc Note in particular that there are six C2 rotation axes (only two are drawn in the figure) perpendicular to the hghest orderaxis,which is a C6 axis. which have more thar one rotationalaxis of symmetry,then the axis of highestorder is dellned In molei:ules astheprincipal axis. Thcrefore, in benzene,the principal axis is the C6 axis. Also, the C6 axis contains,by tlcfinition, a C3 axis and a C2 axis, which are co-axial with the C6 axis. In other words, the following is true aboutsymmetry oPerations:

cez= c31
C 6 3= c z 1

In gcneral,any cven-orderaxis greaterthan order 2, will contain,lower-ordereven axes. For instance,a C4 axis rnustcontaina co-axialC2 axis, A Cg axis must containboth Ca and C2 axes. perpendicular to the principal axis. There are six in Furthermore, benzene,there are more C2 rotation axes of C-C bonds :uch axes; three of which pass directly through atoms, the other three passthrough the centres to your sketch), It is necessary distinguishthesetlpes of axesfrom i.ou shouldtry and draw all of theseaxeson r,rre axis, which is coaxial with the principal axis. Thus, the two typcs of C2 axesare called C2' and C2". C2

2.3

R e fl e cti o n l a n e s P

\\'e have seenhow part of a molecule's symmetry can be describedby rotation axes. Are there other symmetry in terms of ;jcments which we need to considerbefore we can fully describethe symmetry of a molecule operationis \\.nlmetry elements? Well, of course,the answer is yes. The next most obvious symmetry .i'mmetric2lbehaviourupon reflection. mirror plane which bisectsthe Again, we can start with the water molecule. Imagine a double-sided is to :icrlecule,as shown in the hgure on the top of page 8' The symmetry operation of such a mirror perpendicular the plane of the to the :nrcrchange two hydrogen atoms (assumingthat the mirror plane is exactly mirror is ::rrlecule, and that it bisects the angle). The resulting molecule after the operation of the

Beginninggroup theoryfor chemistry

analogousto the symmetry operation of the C2 indistinguishable from the original in terms of shape----exactly rotation axis. Therefore,this reflection plane is anothersymmetryelemzntof the water molecule.

in Reflect plane

Hl

'" O-t-

H,

,"\

H',

Sketchanotherreflectionplane in the H2O molecule.

Answer
hasbeendrawnslightly out of The other reflectionplane is shown below. (Note that the watermolecule the plane of the paperto give it more perspective.)

Reflectin plane

--+
"1

operationdefinedby the plane the This reflectronplane is within the plane of the molecule. Upon the s1'rnmetry it is alsoidentical to the originai molecule. The hydrogenatomsare not in moleculeis unchanged shape,and in by interchanged this symmetryoperation,and the startingand finishing moieculesarc indistinguishable terms thereforethis reflectionplane is a symmetryelement. of shape, to We can seethat the water moleculecontainstwo reflectionplanes,eachperpendicular the other. In group theory a reflection plane is denotedby the Greek letter sigma, o. Thesereflection planes contain the principal 'vertical' along with the principal axis. Accordingly, if a reflection axis within the plane, and can be said to be 'v' means'vertical'. plane containsa principal axis, it is denotedby the symbol or, where

Svmmetm- a start

List all of the symmetry elementspresent in the water molecule. Sketch the elements on a diagram of a water molecule.

Answer
These E, Cz, ov(xz)andov'Oz). Noticethat,in this case, two o, planes distinguished are the are from planethey lie in. The xz planeis perpendicular the plane of the eachotherby which cartesian to molecule, with thez-axispointingalongtheprincipal rotation axis.

c2 AXIS

planes theNH3 molecule. planes a As above, identifythereflection in Sketch of thereflection one on planeon theposition Labeltheatoms showtheeffectof thereflection drawing themolecule. of and of the atoms.

t
I

10

grouptheory chemistry Beginning for

Answer
planes' The NH3 molecule is viewed The NH3 molecule is shown below with one of its three reflection .from aboye, with the nitrogen atom nearestto the viewer. There are three reflection planes in total, each and exactly bisects the H-N-H angle at IZO' to each other. Each plane passesthrough a single N-H bond angle is bisected' The nitrogen and Hu oppositeto the N-H bond. In the figure below, the Hb-N-H" atomslie either side of the plane' the uio,,,, r" in the reflectionplane itself, whereas other two hydrogen the H6 and H. atoms. The other two reflection The operation of this refleition plane is to interchange differentcombinationsof hydrogenatoms' planeswill interchange

in Reflect plane 4

,/''

H{-\
Hb

given the generalsymbol ov. This is because For the NH3 exampleabove,all three of the reflectionplanesare Each plane can be uniquely rdentifiedby o'' o'' and o'" ' all of the ptun.. contain the main C3 rotation axis. to This is analogous the reflection planesin the water molecule' looking at an There are two more types of reflectionplane that we must consider. This rs best done by alound the gold atom' planarstrucrure a Squale example. Considerthe planarmoleculeAuBro, which has

in the molecule. Sketch this of Sketchthe structure AuBrr, and identify the principal rotation axis principal axis on your sketch.-Identifyany otherrotation axes'

Symmetry- a starl

11

Answer
The moleculeis sketchedbelow with its principal C4 axis. It is a C4 axis, as the moleculecan be rotated from the original molecule. Note also that there by 90' (36014) aroundthis axis, and be in"distinguishable moleculethat we encountered to to Ne CZaxesperpendicular the principal axis (analogous the benzene above).

COaxis C, axis

"Br
L-, ?XfS "T""""2Au:"""""' -.\ /.: \__

-Br -Br

.ft:

Br

"""4' c, axis

l,: .'d t?

'see' the to How many reflection planescan be found in this molecule? Perhaps easiest are the reflection planes '.r'hich contain the principal axis. There are two tlpes of such reflection planes. One type, which is marked as or, on the diagram below, contains the principal axis, and also contains Au-Br bonds. Note that there are :jtually two ov planesat 90" to eachother (only one is drawn). The other type of reflection plane is very similar to the ov planesinsofar as they Containthe principal axis, rut they do not contain any of the Au-Br bonds;theseplanesbisect the Br-Au-Br angles. There are two of this rpe of plane, which are given the symbol 6d,'d' standsfor'dihedral'. Notice the similarity of the o, and o7 the :lanes, which are only different because o, planescontainthe Au-Br bonds,whereasthe o7 planesbisectthe tsr-Au-Br ansles.

Br.
Reflectin plane

.Br -Br

+
Br
o

Br

,/o'\

Br
A

.Brb
Reflectin plane

Br

.Br

_>

Br. o

Br

,,/o'-

-r.

grouptheory chemistry for Beginning above' in planes whicharenot shown thediagram and the Sketch AuB{ molecule theo, ando7

Answer

Br/

oy plane

AuBro above,there is one more reflection plane in $e Apart from the o, and o7 reflectionplanes-shown sketch the plane on a diagram of the molecule' molecule. Figure ou, *lir" the new plane lies, and

Svmmetry- a start

13

the This plane is perpendicular to the principal axis, and lne remaining reflection plane is shown above. h.' t.ic r reflection bv tthisp f l p c t i n n

::#ffi:';;;ilt;;;i"J*i,r,i"
il:J:l#k.;;;

* ;:;J; T1i::j1"^1"*::::::ll:l.t",Yl1l',':,3.?"n#,*l?,il ^ ;F.;y*rjrt is givenrhesymbol where'ftistands 'horizontal'. turns:l|,fJ',#,TTI .;;,;; outthatthisis an It for oh,
c c\/mmeffv

operarion rhe rn plane. racr, svmmerrv: + ^ + Ldefinedi l l ,rre n^^:. ir ic cf

-:'"'l'Ji:l,l;il ,ffi;;';",*r,";;i;;

-:;;il";:;;";;;"",

to plane is perpe*ndicular the principal axis' -:nensions. The key thiig to noiice is ttrat the oh

abre ,Ju" toidentirv' ^n1::1"1:il:':.0^1:T:-':::?;3::ti1:Ttlii; .trvou in three rhe.morecure y.:l of mooer AuB{,
^fl^^rlnn nlano

.:o:hu:

_.-T^:::,

2.4

of Centres inversion

to describethe symmetry of a molecule' This ,i'e now come to anothersymmetry element which can be used and it is given the symbol i' The good ...mmetryelemenris cailed a centre of inversion (or inversion centre) rotation axesand reflection planes' a single moleculecan only -;ng about this symmetry elementis that, unlike about it ':\.0 one such centre,and we only need to decidewhethera moleculehas got one or not' Thg bad thing .See'. Certainly, this is one of the cases . lhat the actual symmetry element itself is sometimesdifficult to ..:.e practicemakesPerfect. re T h e r e a r e t w o w a y s t o d e s c r i b e a n i n v e r s i o n c e n t r e . S o m e p e o p l e f i n d i t e a s i e r t o u n d e r with d o n e w a y r a t h e r s t a n practice' ,seeing' an inversion centre is by inspection; this gets easier --.n the other. The first way of Take AuBr ' as the example again' To :.:rer a while, this is the quickest way of spotting an inversion centre' line ' one has to imagine moving e*achatom in a straight ,:.e the inversion centrein AuB{ by inspectio"n, away from the Ax atom in the same .* ards the Au atom, putting ,nfougtt tit" Au atom, and then moving away from the Au atom as it was before the symmetry -.:ectionto a point wfreie the atom is at the samedistance Au atom' :eration began. The inversion centrelies on the

centrewith an andlabeleachBr atom. Mark thepositionof the inversion molecule SketchtheAuBr, rhe and above, sketch result. as operation described ;;;.' fu..n ouf,n. inversion

grouptheory chemistry for Beginning

Br'

,/\\

-Br \
\

d\c

position at all' The bromine atoms' on the Au atom does not changeits of course,carrylng out this operation 'opposite' bromine atoms' SinCethe final result after inversion is their however, are all interchangedwith as a symmetry element' then AuB{ has a centre of inversion indistinguishable fromtir. &iginuf , centfe' using the methoddescribed should alsohelf in identifying an inversion The following two exarnples above.

using the method (E)-1,2-dichloroethenear":::lj: (octahedral), For NH3,(Z)-r,2-dichroroerhene, has an in'Ersion centreof symmetry' If the whetheror not eachmolecule above,reason described operation' inversion of the and labeltheatoms sketch resu-lt the centIe, haveaninversion does molecule

Symmetry- a start

15

Answer
centres symmetry.Theinversion of and centres are Only (E)-1,2-dicNoroethene CoCf]- haveinversion bondanddn theCo atomrespectively. Carrying the operations these out in themiddleof the double on is molecules shown below.

inversion

+
ob

CI

O - inversion centre

Inversron

---+

CI

The second way to identifyan inversion (If centre to usea slightlymoremathematical is description. the worriesyou here,thenyou canusethe qualitative :athematics definitiongiven above, worksjust as well. it you shouldreadthis part anywayto seeif you can understand The mathematical l"rwever,if possible, it.) -:scriptiongoesas follows: if the inversioncentreis placedon the origin of a three-dimensional cartesian ("r, positions givenby the coordinates y, z), thenan inversion set - tordinate of axes,and atomsare at general (-x, element that molecule a molecule of if havingthe sameatomswith coordinates -y, :entreis a symmetry -:) is indistinguishable the originalmolecule.An example from helpto makethisclearer.Thediagram should placedon a set of cartesian .: the top of page16 showsthe AuBro molecule axes. The Au atomsits on the is :rgin(0, 0, 0). Eachof the Br atompbsitions givenby a uniquesetof coordinates; for Bru let us define so, placed the origin, centre with the symmetry :e coordinates (-ru, z). Theinversion as operation, element at !a, each thecoordinates follows:as ;arsforms of ('' Y'') -:-'(-'' - Y' -')

:rrr example, Br" atom coordinates the after the originaloperation become(-x",-y., -zc). Sincethe new haveidentrcal of of :.rordinates eachof the Br atoms values coordinates oneof the otherBr atoms-so. for to is :rample (-xc, -yc, -zc) = (x^, ya,za)-then the molecule after the symmetry operation indistinguishable is for :om theoriginal. Therefore, inversion the centre a synrmetry element AuB{.

lo

for Beginning Srouptheory chemistry

Br.
a

Bto y

inversion

Brc B r.

-..4"f
Br

./i"f
b v"
IX

1' Br
aY

lv

V^ ,/

'

,,

(x., y", z")

(-x., -Y^,-r^) = (x", f", z")

A t h i r d , b u t s o m e t i m e s u n r e l i a b l e w a y i s t o r e a l i s e t h a t a n i n combination t r e i S e x a c t l y t h e s n by plane. This v e r s i o n c eis rotation 180' axisandu-rp!"in. reflection rotation a combinafionof specific words,if a molecule In other to planeperpendicular the rotationaxis. in a reflection alsohaveal fottowedby reflection to-thisaxis' thenit must'by definition' planepe'peodlcutar ls contains ac2axisand a reflection cenffeelement inversion not be the principalaxis.) The centreof symmetry.(The cz axrsneed inversion of presence an inversion plane, But, BEWARE,the reflection point of the axis andttr.9 at placed the meetlng reflectionplane a perpendicular *ru" ,r,"i,rr" .or.iur. hasa cyaxis and doesnot necessarily of centre symmetry elements' asindividualsymmetry

U s i n g t h e m e t h o d s o n p r e v i o u s p a g e s , r e a s o n _ w h e t h e r o r n o t t h e H 2 o m o l e c u l e thekeyn v e r s i o n c e n f f e a S moleiuleandh a s a n i svmmetrv

Do element? thelm.e f9r 'lufro a symmetry

nor Oltlq*-ltLthe

it ha3 an inversion centre or not' elementswhich help you decide whether

Svmmetry- a start

l' srver
HlO molecule has a C2 axis and two mirror planes, but neither of these mirror planes is l: -:::i:'idicular to the C2 axis. Despite the fact that the molecule does not have a mirror plane -,:- i:dicular to a C2 axis, we cannotsay for definite that the moleculedoesnot have an inversion centre :. xrfletry. We must use the other dehnitions to decide. Using the first definition: if, the origin is I ::3J irn the oxygen atom, and the hydrogenatoms are'moved'towards the oxygen atom and then -- ',ed' away from the oxygen atom in the same direction to the samedistanceaway from the O atom, --::. e different orientationof the water molecule is obtained,see figure. In fact, it is impossibleto pick .:'. rri-einwhere performing an inversion centre operationgives a molecule indistinguishnble fromthe ^._l;nal. Therefore,the water moleculedoesnot have an inversioncentreof symmetry.

inversion aboutO

.H."o\,o

'\o "'
^ HoO* *o
b Hr

-rH

,l
o6 Plane

AuBro doeshave a C2 axis (coaxial with the principal C4 axis) and it does have a reflection plane .Jrne?s <it) perpendicular the C2 axis. Therefore.fie moleculealso has an inversioncentre. to

ica
\,

a n dc2 AXES

,:r the exampleabovethe inversioncentrelies directlv'on the Au atom.

Which of the following moleculeshas an inversioncentreof symmetry? NO;, SOl-, H2O2, PCl5, benzene, chair-form cyclohexane, boat-form cyclohexane, Niclf, NitCN)i-

18

g,roup theory chemistry Beginning for

Answer
H2O2 only has an inversion centre when the molecule is in a planar E (or trans) configuration. The inversioncentreis then in the middle of the O-O bond. Benzene-in the centreof the molecule. Chair-fgrmcyclohexane-in the centreof the molecule. planar)----on Ni atom. the Ni(CNI (square

It is important that you can identify an inversion centrebefore you progresswith the rest of this book, as it will 'seeing' the inversion centre,then it is well worth be referredto again and again. If you have had difficulty in in building someof the moleculesdescribed the questionabove,and seeingif you can find the inversioncentrein threedimensions.

2.5

rotation axes lmproper

This now brings us to the hnal symmetry element(and operation)that we need to know. I am often askedwhy this particular symmetry element is neededin group theory. The best way of answeringthis is to consider an molecule,CHa. It is easyto seethat examplefrom a qualitative point of view. Considerthe simple, tetrahedral in this molecule are in identical chemicalenvironments.In other words, the hydrogen all of the hydrogen atoms atoms can be related by some single symmetry operation. That is, there must be a single symmetry operation that we can carry out which will transform each of the hydrogen atoms to all of the other hydrogen atom positions. This is exactly analogousto the C2 axis in water relating the equivalenthydrogen atoms,and the C3 axis in NH3 relating all of the hydrogen atoms. However, if one attemptsto relate all of the hydrogen atoms in methaneusing our existing knowledge of rotation axes and reflectionplanes(the moleculedoes not contain an inversioncentreof symmetry)it is impossible to find a single symmetry element which will allow us to transform each of the hydrogen atom positions into all of the other hydrogen atom positions. So, for example, the C3 axis which is present as a symmetry element (see diagram below), describesa symmetry operation which transforms only three of the hydrogen atom positions onto each other; the fourth hydrogen atom on the rotation axis, cannotbe transformed ontg the other threepositionsby this operation. Clearly, we need anothersymmetryelementwhich can describe a symmetry operationto relate all hydrogenatomspositionsto eachother.

Enter the improper rotation axis. This is a single symmetry element,the operationof which can transform each of the hydrogen atom positions into all of the other hydrogen atom positionsin CH4. Unfortunately, this symmetryelementis the most difficult to identify, and requiresquite a bit of practicebefore one can be confident this is to start with an example. using it. As before, the best way of approaching Consider methaneagain. The molecule has two types of rotation axes, C3 and C2. One of the C3 axesis identifiedabove.

-l
rhe I

Symmetm- a starl

19

__l
.. it will : . wOrth - Jntrein r:.1 why .! Jer an .rc that I _rogen : -:atlon t: atom

>ietchthe methane molecule, and identifythe positionof one of the Cz axesof symmetry. (A small :.olecularmodel may be useful here.) Label the hydrogenatomsand sketchthe effect of the Cr .\ mmetry operatlon.

Answer
()ne of the C2 txes can be seenif the moleculeis viewed with the carbon atom in the plane of the paper, :nd two hydrogenatomsgoing into the plane of the paper,and two hydrogenatomscoming out of the :lane of the paper. The view is looking right down the Cz axis. Notice that rhe C2 axis bisectsthe H-C-H ansle.

: rec3
.!.tu6L

l"
i
:

:" it is i rt0m t: asa : ithe ,; :med r . -'ribe

c2
"b

H i'
:

H;-Q-H

d : ui"b:d

-'4
i H^

Hc

Using the C2 axis, only Hu and Hc (or H6 and H6) atoms can be rnterchanged. It is impossible to - .:rchange H" the and H5 atoms. For instance, clockwiserotationof 90' (not a symmetryoperation itself a in : CHa) doesnot give an indistinguishable result,as the H atomsare on oppositesidesof the plane of the paper - :r wherethey would give an indistinguishable result (seefigure below).

H"
u;-Q-H
Hc
brm ; his [--Jnt !-. is

90'rotation -+

ilo I
H''.....''C''....-''H cla

I
H
b
But, a rotation of 90o almost gives the right result. If we now combine the rotation by 90" with reflection - .l reflectionplane perpendicularto the axis of rotation (so, in the figure the reflection plane is in the plane of --; paper),then we obtain a molecule which is indistinguishable from the original (see figure below). In fact, -'..scombination of operationsgives us a single operation which is a symmetry operation for the molecule. fr :e. however, that the molecule does not necessarily have a either C4 axis of rotation, or a reflection plane as

20

Beginning group th'eoryfor chemistry

in a individual symmetry elements. (This is analogous to the combination of C2 followed by reflection presence an inversion centre does not necessarily of reflection plane for an inversion centre of symmetry. The imply that thereare individual C2and reflectionplane elementsof symmetry.)

l"
H-C-H "d
: : :, Hc b

90'rotation andreflection

!o
ci'
"b

reflection plane gives a new symmetry element, The combinationof a rotation and reflection in a perpendicular In the example given above, this axis is given the symbol 54, which is called an improper rotation axis. = the because rotation is 90", and 360190 4. there is a couple of importantpoints about improperrotation Before we move on to try some examples, applicationsof an improper rotation on a molecule. For axes. First, we need to study the effects of successive is ttre effect of applying the 54 operation once, twice, three instance,take the methaneexample above; what represenl times or four times in succession? As with the rotation axes, we can use the following notation to = S41, two operationsS42, three operationsS43 and so on. The 541 successiveoperatlons: one operation operationis shown in the figure above.

Using the methaneexample shown above, sketch the molecule with labelled hydrogen atoms and show the eflect otS+2 and S43 operations.

Symmetry- a start

21

Answer

H"

so'
H-C-H
o:

Hc

H,

so,
H;-Q-H

:o :

--.

542 operationis exactly the same as the C21 operation,and the S4a operationis the same as the E ::rrion. Therefore,the only unique symmetry operationsfrom an 54 axis are S41 and S43. Notice, therefore, : .. ,n 54 axis must have a coaxial C2 axis as a symmetry elementin the molecule. In fact, without taking the : ,: much further, it is true that for any even-orderS, axis, there must be a coaxial Cn12axis. which can be applicationof the improperrotation also leadsto operations For an 56 axis, the successive -.- - : hcdby othersymmery operations.

can be described on 56 ?ertormsuccessive operations a generalmoleculeand figure out which operations e.g. 562 is the sameas C3r :r other symmetry operations,

Answer

562 is ttre same as C3I 563 is the sameas i 564 is ttre same as C32 566 is the sameas E Only 56l and 565 are unique

The Sz operationis unusualinsofar as it is exactly the sameas carrying out an inversion operation,since it reflection plane. (Seethe sectionon to - ::esponds a rotation by 180'followed by reflection in a perpendicular r-jgSof inversion.) Accordingly, the 52 operationdoesnot concernus as chemists. .:

rotationaxeswith odd orders(e.g.S:, SS,S2...)requirea little more care. Taking 53 as an Improper is , ::rple. The problemhere is that the S33 operation not the sameas the E operation.In fact, the S33 : rotation an the that You can'see'thisif yourealise performing improper operation. to _:;ationconesponds a o performed, means whichnecessarily that has number reflections been of means an odd that of .,:: number times, to --: resultof S33 is a reflectionin a planeperpendicular the improperrotationaxis. However,the Slb

22

Beginning group theoryfor chemistry

operation(i.e. a double rotation) is the same as the E operation,since now an even number of reflections has been applied. Without going into the details of which other symmetry operations are the same as S3n operations listedbelow. are the operations, corresponding S32 is the sameas C32 S33 is ttre same as o S3a is the same as C3 536 is the same as f Only 531 and S35 are unique symmetry operations. A similar argument applies to other odd-order improper rotation axes. These are not describedhere, but the 'take-home message' is that many of the improper rotation operationscan be described by other symmetry and that with odd-orderimproperrotation axes,S12'is the sameas E. operations, Now try the following examples:-

PC15has a trigonal bipyramidal structure. Sketch the molecule and identify the improper rotation axis. By labelling the fluorine atomsshow the effect of the S operation. (Hint, first identify any rotation axes.)

Symmetry- a starl

23

Answer
The 53 axis is coaxial with the C3 axis.
a

*U
a

C, and S.

F"
F
d

In
F

F"

Ttr.'
Fb

Tt,"
Fa

F'

itr'
Fb

srt
F
elF

s,t

f'
'

Io
F
',\ d

t\

Fb

srt

seo

srt

'see'. This is an Identify the 56 axis in CoCl]- (an octahedralcomplex). This can be a difficult axis to axis and it must have a coaxial Cn12axis. Therefore,it is worth looking for improper rotation" even-order '-hecorresponding C3 axis first. A molecular model is useful for this example. Sketch the molecule ','rewed down the C3 axis, and by labelling the chlorine atoms,show the effect of an 56l operation.

Answer
r I f t h e m o d e l i s v i e w e d i n t h e c o r r e c t o r i e n t a t i o s;, t(and i:) e s 6 a x iThe effect ofea 56 i toperattontsS e e t h e n h e n t h axis' s c a n b e s e n q u e c l e a r l y . whictr ts viewed directly d.*;;; diagram below, shown'

you can describe,T.r;di]:Tl5i*:rjuJ:;TJ ffiT:il:T#J"J1';il; morecuresnow of

y ur tne :, You cannow descrtbe syrlllrlsu with practtct andit is worth of molecules. gets easier *y*t.W elements of idenirfylng *i;ili; The elemenrs. andoperations' exampies symmerry 'seeiig' all of thesytmet'y etements in examples these with, unrrry;;;" confident attempting persevering Before ut id";;i?;; tfiti':li]ements' that ro elements we have designed give you pracrice beloware does.The symmetry eachor trresymmJtryoperations makesurethatyou *oJrro"o what are: studied Cr) axes(sYmbol Rotation o) (sYmbol Reflection Planes i) (sYmbol centres Inversion S,) (sYmbol rotations ImproPer
Identrfy and list as many symmetry PCl5 (trigonalbiPYramidal) (E)- 1,2-dibromoethane CH+ molecules: elementsas you can in the following

which are used to describethe symmetrl symmetryelementsand operations This brings us to the end of the @rJ'rv^v-..'- -

Answer

thereare 3o'' (More completely' 53 tl:TT':-E' C3' 3C2'o7x' and symmetry PCl5 hasthe followrng Sr1 53 operations andSl)') *t"ct''are C3f andc*'aniini'"ut"two two C3 operations, E' elements: C2' i ando;t' symmetry has (E)-1,2-dibromoethane thefollowing

CH4hasthefollowrngSymmetryelements:!,,,,C2,54ando4(thesearedihedralplanessinceth bisecttheH-c-Hangles).ThereareseveraloreactrofthesymmetryelementsexceptE'

Symmetry- a start

25

2.6

identity, inverse class and operations, Successive

operations a in of 3eforewe go further it is importantthat we look at someof the properties symmetry furtherour properties be required section wherewe will build on themto develop will in 3, rolecule. These of -nderstanding grouptheory. Most of the resultswe come operations. of In this part we will studysomeof the properties symmetry they heresimplyhaveto be remembered, do not haveto be proved. :Jross

operations 2.6.1 Successive

-ie first question to ask is: what happensif we carry out successivesymmetry operations? We have already seen combination of rotations with reflections to describe improper rotations (rotation followed by -^te successive -:tlection), but what about any combination of symmetry operations;for example, is there any difference between . foration followed by a reflection and a reflection followed by a rotation? In other words, is the order in which .i e perform operationsimportant? Again, this is probably best illustrated by an example.

PH3,has a pyramidal like the and structure NH3. Sketch structure Phosphine, of elements the structure.
:.e y r i its i rrth : .pl e s : . tl c s .]ave

the symmetry

Answer
PH3hasE, C3 and3o, symmetryelements.

and by labelling the hydrogen atoms show the effect of performing Again, for PH3, sketch the structu-re, following combinations of symmetry operations. (Use the same orientation of reflection plane in the eachcase.) a) oy after C3l. U) C:l after ou.

_t

10

grouptheory chemistry Beginning for

Answer
planeis theone atoms'Thereflection on belowwith labels thehydrogen is ThePH3molecule sketched afterC31andthebottomscheme o, performed shows thatlies in theplaneof thepaper.Thetop scheme afteror. C3l performed shows

6v

P-.... \Hb

.'H
b

-P....

Hc

,/ H

\
a

cH

6v

P-.... Ha \Hb

p ...

+./'\ H\c a
c

H to

cu' +./=\
H.\ o

D ._

n
H.

in operations a differentorderdoesnol give symmetry showsthat the resultof performing The exercise is the operations: orderof combination symmetry rule for combining general this results.Indeed, is a identical we example haveshownthat: with the above Takingthispointa little further, important.
performed after C3l C3l performedafter o, doesnot give the sameresult as o, replacethe in This can be exPressed a more mathematicalway. If we sign, then we get. 'performed after' with a multiplication

C31 performed after ou can be written as: C31 x ou and o, performedafter C31 can be written as: o, x C31 as' 'same as' is replacedby an equalssign '=', and 'not the-same is replacedby a not equalssign If we say that algebra)-then we can write the following .*, -also, let us dispensewith the multiplication s-ign(as in normal be true): for this example(for other examplesthis may not necessarily C3lo, * ouC3l the First, we have expressed symmetryoperations There are two things to rememberabout this particularresult' which is performedsecondis operation way. (Notice here that, in the equation,tLre in a more mathematical if easierto understand the symmetry This may soundlike an odd way of doing things,but it is written first. i 'operates whateveris ti tt e right'' So, for example' C3l c' can be read as C3 on operationsymbol is read as takessome getting used to') operations on operates the result of ou. This way of writing symmetry property of the order of performing an operation being second, for the mathematicians,this g.nrrut come back t0 this in the next section' and it simply important is called a non-commutativeproperty. we will needsto be rememberedfor the moment' operationsis important' The combination of So, we have seen that the order of performing symmetry result' The result of any combination of symmetry symmetry elementsalso leads to the following important molecule' So' for the example abovewe can can be describedby a single ,y*rn"tty operationof the operations say the following:

Symmetry^- a starl
6y C3l = ald C31 cu = ou" ou'

21

in of operations the otherreflectionplanes the molecule. Whereov' ando, " arethe resultsof the symmetry to that Theeffectof o, C3l is illustratedbelow(remember the hrst operation performis the oneon the right)

P .... \Hb

crt

+
H
c

P.... \Ha

\'
\

l6v
t\
"H H
a

resultto reflection in by of shows theoperation C31followed reflection ou givesanidentical that Thediagram the the in or' (or' is thereflectionplanewhich contains original P-H6 bondandbisects H.-P-H" angle). In operations of that operations a molecule anycombination symmetry of resultof symmetry iact,it is a general Thiswill be left asa general operation. is as a withina singlemolecule thesame performing singlesymmetry resultto be remembered-wewill needthis resultin thenext section.If you arein anydoubtaboutthe truth of to PCl5is a goodmolecule try in thisrespect. for try fte statement, a few examples yourself; threesuccessive symmetry whataboutperforming two So far we havecombined symmefy operations, operations?

For the PH3 examplegiven above,what is the effect of combining the following operations?Remember that ov is the reflection plane which lies in the plane of the paper, and ou' is the reflection plane which conta:ns the original P-H6 bond before any synrmetry operationsare carried out (i.e. this reflection plane 'move' with the P-H6 bond during the operations). The parentheses the last two examples in does not must be carried out before any other mean that the combination of the operationsin the parentheses combinations, following the same rule when combining two operations that the one on the right is first hgure out what single symmetry operationis the same performedhrst. (Hint: with the parentheses, as the combination of the two operationswithin the parentheses).It will probably help to sketch the molecule with labelled hydrogen atoms in each instance. C 3 1o u ' o u or'o, c3l (C3l or) or' Cgl (ou ou')

28

grouptheory chemistry for Beginning

Answer
c 3 1o r ' o ,
to. o,'o, corresPonds This can be singleoperation this Splitting up. We hrst needto figureout what as out doneby sketching themolecule follows:
I

6v

oy

o\
H
c

bH'

' a

,/r\

il.
Ho

-+
H
,/ bH

,P -.... \
a

Hc

' = From the ftgure, it can seenthat ov 6v C32' J czrt*'which trtu'^c]f"'\t" Therefore,we can "y answeris:Ca1or' 6v = E The other answersare:g ou' ou C31 = C32C31= ( C 3 1o r ) o u ' C3 I (o, ou') = C3l C3l = Czz

can similarly be worked out as

= E' so' the

Althoughtheanswersaboveareforaspecificcase,theyillustratetwoimportant'and'asitturns is are First, ihe orderin which operations combined still of properties symmetryoferatlonsin moiecules. is showthat the sameanswer the last two examples important-i.e.they u." ion-.ornmutative.Second, that this order.In general, means the partsin a different workingoutdifferent despite (CzL inthiscase) obtained operation): synrmetry any denote paflicuiar A, followingis true(where B andC A(BC) = (AB)C ts operations associative'This is simplya of that the combination symmetry this To mathematicians, means nameforthistypeofmathematicalbehaviour,andjustneedstoberememberedforthemoment.

2.6.2 ldentitY
the part of describing of doing nothing'E' is an important that we have alreadyestablished the operation of other symmetn' canbe seenas the result of combinations , symmetryof a molecule. For instance E nextsection, for remembered now,aSwe will build on it in the to needs be This operat,ions. tact,again,

2.6.3 Inverse
the following is alwaystrue (where Another property of symmetry elementsis that molecule): All is atso a svmmetrv operationof the ;;;;;;i;"";; A is any particulal symmeul

A-rA = E

has ooerations aninverse.

SymmetrY-a start

29

operatlons symmetry of Writetheinverse the following

Answer
own inverse)' E E hasinverse (it is its C3z Ca1hasinverse

t"]:T"-t7i-^in, czznas inverse). is irsown has inverse ov (agal ir o,

ffimmetryoperationn?lulinverseop^erationwhichisalsoasymmetryoperationofthe sectlon' this we und will use in thenext is :...rleculea general "'uf'

2 . 6 . 4C l a s s

can svmm:ffvoperations motecuie'These 3l.now'youarehopefullyfamiliarwiththenotionthattlresymmetryofamoleculecanbeexpressedintermso molecule in rl1:1,.r.;;;;;il* oPeratrons a y operations :itt'e . :ollecdonor .yn}rn"t For ."u,nprJ,itr"-tvr1i1v^ of ot tr,esymmetry tt e motecule. (not'ap,9ol, several these point of view be :-.en usedro t erpcedne qualitative and.; i*,o",o, C31alrdC32arc similar,and E, " *1.' tnut tr'"y;;'i;;;. .ie NH3 are C3,, in the symme;;;J;;", arJ .\'mmetlyoperations simltar '.'"r; calleda similarity procedure'. similar' E is by itsel{' nathematical .itn br" arealso : which hasthe molecule s..''Nn'"f-d ;oeed' any t"il t^"'' E,2C3 and3ou. canbe og"n.u oi,v'In"ov opjT.l:i''similarsymmery operarions --.at iorio*ing classes C32ue \n the2C3 can and op".u,l6o,) be ,'o]:.1'"]"-* .'me Symmet,y op"'ution'ut" 'n 'ftu' clasi-C31 '3' denote lnOiviOuat how many .rherethe ,2' andthe

',:;:H::it#nt*uili";"#T$,ffi iliur*,voudoneed'[okn :,T"',T[i,',{*ffi

svmmetrv . *11"-:I:r orthe that o'au.J""'*t:ft^-,t::Tl,J:";::i:?ifr:Jrog - rss(Nore this operations classes it"l^::ii:J;tfiit#;*ti*v r'uurng operations also into withina class
tv*"ttj Putting
3\t sectlon'

orin u'" i'i '1he ::rl,Hi,,i"fr:#$?ffi*'3,''l'';1"J:irx'n";T'Jl"'#ff13il:Tl*;T

groups Point

2.7

:]isisnowthelastpartofthissection,Here,saquickrecaponwhatwehavecoveredsofar:

.Rotationaxes,reflectionplanes,,"l:iYcentresandimproperrotationaxesareallsymmetryelement

operations' orits ' r behavrour' ,"rms svmmetrv io . n;"*XX;3ffi:11'J'1"-r'S":tT1":iio.o,n rules, grurumarhemaricallike *rrain .o*uro"o?"ra*,",
. Thesymmetry "nJ;l#;il"
]:ese facts now

make in more detail' and we will at the Symmetry of molecules to lo^oking to becumbersomehave write provide a foundation lor

;i;;;"*r use :Jpeared of rhem.ff"

*u, oi . a shorthand
rr.trfihafl d method works'

".t;*sil.. tim" *::'j; eu"'v -: f ry.'t11*lti},1#'ffi ;:':tT"jl-lil: operations a' tr,e .ir or symmetrv 'l: symmetryof molecules'In ,lpr-.r"otiog the

.f

6;;;',Y.::,*;;t'

can

Beginning gr oup tlteory fo r che try mis List all of theuniquesymmetry operations you canfind in a PCl5molecule (trigonalbipyramidal). that It will helpto sketch molecule, a smallmolecular the and modelmayalsohelp.

Answer
Thesymmetry operations are: E, Cl , Czz,Cz Cz' Cz", oh, 531 s35,o, oy' oy" havebeen missed as Noticethattheredundant symmetry operations, asS32whichis thesame C31, such out. Thesymmetry elements shown are below.

.:)
a

C, and 'S, axes

CI
Cr' axis

CI

CI
Craxis

/;;-r
CI

;'i\

oh

6v

lcl
CI

is operations clearlytoo timeall of its symmetry by of the To describe symmetry a molecule listing on being able to identify key tvtttl is used' It relies the consuming.Therefore, following ctassir,calioo

Symmelry- a start

31

...:.metry elementswithin a molecule. The key symmetry elementsthen define a particular group, which has .;'.ir&l different symmetryelements. So, for example,to classifythe PCl5 molecule,it is only necessary to -;:riiy the principal axis of rotation, the perpendiculu C2 axes of rotation and the oh reflection plane. This :\3s away the drudgeryof having to identify every single symmetry operation. All of theseclassifications have ,::r worked out beforehand, and all we needto do is to follow the rules for getting to the particularclassification :-'ebelow). Each classificationis given a symbol, which uniquely identifies that classification. Each symbol standsfor what is called a point group. The two words . : ilection of symmetry operations. The symbol also represents - ,:, and group each mean something. Point means that ali of the symmetry elements associatedwith the .:.metry operations passthrougha singlepoint in space. This point is not changed positionby any of the in -..:,metry operations. For example,the 'point' in the PCl5 moleculelies directly on the phosphorus atom. 'point' for 3:n are,however,it is not necessary the of the group to lie on an atom, e.g. H2O2) The word group .:ins that we have a group of symmetry operations.We shall seein the next sectionthat we can define group a :',rematically,but for the moment it is sufficient to recognisethat we are dealing with a group of symmetry in - J:.1tions eachpoint group. We classify a molecule into a point group by answeringsome simple questionsaboutthe molecule. . - ; s t i o n1 . :ite nnlecule is one of thefollowing'recognisable' groups
ii ):

:ES

Go to question2 given the point group symbol 07, octahedral, given the point group symbol T7 tetrahedral, linear, given the point group symbol C-v (if it does not have an I symmetry element) linear, given the point group symbol D-2 (if it also has an I symmetry element)

- j c s t i o n2 . - ,. es the moleculepossessa rotation axis of order 2 2? ':ES: \il: Go to question 3 If it has no other symmetry elements,then it is given the point group symbol C1 If it has one reflection plane of symmetry,then it is given the point group symbol C, If it has a centreof inversion,then it is given the point group symbol C;

{ i e s t i o n3 .:,.tsthe molecule more lhan one rotation axis? ':-ES: \t-): Go to part 4. If it has no other symmetry elements,then it is given the point group symbol C, (where n = Ihe order of the principal axis, e.g. C3). If it also has one o,6,then it is given the point group symbol Cn7, (where n = the order of the principal axis,e.g. C2p). If it has n oy, then it is given the point group symbol Cru (where n = the order of the principal axis, e.g. C3r). If it has an 52, axis coaxial with the principal axis, then it is given the point group symbol 52,

l,

,nolecutecan be assigneda point group asfollows:

If it hasno othersymmeffy elements, it is giventhepointgroupsymbolDn then (where = theorderof theprincipal n axis,e.g.D3). planes If it has Sotn 64 reflection bisecting C2 axes, thenit is giventhepointgroupsymbolDn7 the (where = theorderof theprincipal n axis,e.g.D4l. If it alsohasoneo7r, thenit is giventhepointgroupsymbolDn7, (where = theorderof theprincipal n axis,e.g.D31). This series questions of allowsus to identifyall of the commonpoint groupsencountered chemistry. in pointgroups, fortunately pointis it important you llere areotherpossible but thesearerue. As a starting that (for pointgroups; -.n recognise some speciltc these the07,(for octahedral),Ta tetrahedral), for a linear are C-v --rleculewithouta centreof symmetry (e.g.HCN) andD-7, for a linearmolecule with a centreof symmetry

32

grouptheory chemistry Beginning for

in and are (e.g.COZ). Hopefullyall of thesecases easilyrecognisable, it shouldbe a fairly simpleexercise to that the assigning pointgroups.Note,however, for a molecule be in the O7,or theT4 point groupit mustbe pointgroup. to be ifit respectively, is not thenit should assigned a different or perfectty octahedral tefahedral help. belowshould quicklygets and groups with practice, ttreexercises better these Identifying

the above,assign point group of PCl5. It mav helo to refer back to the symmetry Usingthe questions in PCl5thatareshownin the previousexercise. elements

Using the questionsabove,assignthe point group of NH3.

Answer
PCl5 1. Question pointgroups. not and shape does fall into anyof thespecial bipyramidal PCl5hasa trigonal 2. Question the through linealF-P-F palt of themolecule. YES:thereis a C: axiswhichpasses 3. Question axis. to whichareperpendicular theprincipai YES:there C2axes ue 4. Question it o, It elements. hasttrree planes.However, alsohasa o7, has othersymmetry The moleclrle several it to plane. Thereicre, is assigned pointgroupD37t.

NHs 1. Question pointgroups. not and shape does fall into anyof thespecial NH3 hasa pyramidal 2. Question YES:thereis a C3 axis. 3. Question C3 otherthantheprincipal axis. axes NO: thereareno otherrotation elements.It doesnot havea o7,plane,but it doeshavethreeoy planes. It doeshaveothersymmetry to it Therefore, is assigned point groupC3r.

is if For within a molecule. example, a molecule for elements are Thepointgroups shorthand thesymmetry E, elements: 2C3,3ou. It is a very' to assigned a C3, point group,thenit hasall of the followingsymmetry It accurately. is the that partof grouptheoryin chemistry you canassign pointgroupof a molecule important

Symmetry- a starl

33

- - .:leiy worth spending time practising this aspect of the subject until you are confident of assigning the . .::.: point group each time. Try to assignthe point groups for all of the moleculesin the exercisebelow. point groups to the following molecules: rrsi-Qn

1 O , P H 3 , S O 2 , H C l , A u B r4,0, C o C l i , (E)- I,2-dibromoethane), benzene, methylbenzene,

? r* ::ehloromerhane. SO1-, HCCH,BzHo, Co(en)', (en = l,24iaminoethane), -O 2CCH 2NH ] NO-, 34

Answer
HlO (C2u),PH3(C3u),SO2(C2r), HCI (D-ft), AuBro(D+il, CoCrl- (On),@)-1,2{ibromoerhane (Doa),methylbenzene (C2r), trichloromethane (C3u),NO" (Dra), SOI- ff a), HCCH C27,), benzene -O2CCN D-1), B2H6(D22), Co(enl]*Oll, glycine(depends theconformation, if the partis on but part 'il planar, oneof thehydrogen and atomsof the ammonium is alsoin thisplane, thenthe molecule planeandit is assigned otherwise is Cl.) reflection :as a single Cr, it

23

Summary

-- :ls sectionwe have seenthat our qualitativeunderstanding the symmetry of moleculescal be made more of --:rtitative by determininghow the molecule is symmetric with respectto severalsymmetry operations. Each - .eculecan be said to contain one or more synrmetry elements,which completely describe the symmetry of the - .ecule. Molecules can also be classified in point groups. A point group is simply shorthandfor the - ..:ction of symmetryelementsthat describethe symmetry of a molecule. We can determinethe point group of - :. ,,lecule answeringseveralquestions by aboutthe symmetryelementsof the molecule. We are now in a position where we can classifymoleculesaccordingto their symmetry and also describethe with tiese symmetry elementsappearto ":.netry elementsof a molecule. The symmetry operations associated w mathemitical rules like multiplication. The question now is can we make the transition into fully - j::isenting the symmetry operationsof a molecule mathematically? If we can, can we then make quantitative -:: jlcdons abouthow symmetry affectsvariousenergylevels in the molecule? The next sectionshowshow this - . le done. What are the main noints of this section? The energy levels of a molecule are linked, in some way, to the symmetry of the molecule. The symmetry of a molecule can be describedwith symmetry elements. operations, described symmetryelements, by can be carriedout on a molecule. S1'rnmetry Rotationaxes,reflectionplanes,inversioncentresand improperrotation ixes are symmetryelements. The symmetryoperations a moleculehave mathematicallikeproperties. of Eachset of symmetry operations an inverseand identity. has but The combinationof symmery operations a moleculeis non-commutative, it is associative. on it Every moleculecan be classifiedinto a point group which completelydescribes symmetry.