GRoup TrrnoRv

Curprrn 4: SvunnntRy 'lNp

' 'l
1.1 a.
' Ethane in the
:jY11jl.,ifJiil:%T3ff::?tr'l$i"i:'",';:4.j3.:";;;'ffij;;;
AXES I
opposite sides of
staggered'co"f9T::i:l::'^?'?:il"'i8tT'fi:':i?;'"X"fflffiifr':i
No r,1,,364,t, Su' ou"tull'aD3lmolecule'
the two C's.

b:l::Tili,xril3;1t'i,fr"'i""1,,:T,:Xi-".,:,T*[T'3;lJlt"oi,'T::ff"#::l;::i
a D31' molecute'
o' und 3oo'' overall'
the two C's' Mirror pfunt''intf"Jt c's'
through both

c. chroroethane
the Cl' and the
,h.*
oPPostte
:3:ff:"j;:1?#t-bi:illt]
n
ilLTil--,prane'

d.l,2-dichloroethanetnthetransconformationhasaC2axisperpendiculartothe
c,., unju'"inuli.ion ..n....'ou. ra||, a C21,molecule.
c-cbondandperpendt;;;,h.nraneor93tr'fi'"tao:ti:^t;io7'planethrough
both Cl,s and both

42 n i:Tfi:ilTi;:XTil"5il5;:i1"'*TT#illil':fi":r:llTH:*fl':;ill;:;;
il;;;t' overail' a Dzr' rnolecule'
two oo' planes (arbitrarily

b.Chloroethyleneisalsoaplanarmolecule,withtheonlysymmetryelementthemirror
a G molecule'
p#;;il; molecute' t't'"ttrott'
with the t. t l"i1'^xtff"il:TiJ itlll,ii;
a
c. 1,1-dich1oro.,hl1:"".1T
one the prane of
the *i..ur"
cTaxtscoincident
and one perpendicular
to the plane ot

o"irtlJ'^ overall' a c2u molecule'

c,s-1,2-dich,oroethy,enehasifi
tftt *otttut"'Yo tT..ule ;il,llffi l",i:EliJ[f=!f ?lT"i'l'F:l{:lti
th" ;-C bond)' Overall
a molecule' C2u

mott and perpendiculff

to the Plane of the
the
has
to
a c2axrsperpendicularplane 9-t'H|'f;it' *ot"t"tt'
in the pt
rans-r,z-dichloroethylene **tt"t': minor
perpendicular to the ot't"" "itnt a Czn molecule'
-

ut'd un inversion
ttn'"i' Out rall'

4.3^.2;"JJ:::lilti;?::;Tilf;1,*'#ff,:1"$:fi,'*:ff:ffi",:il"T*J**
Overall. a D*r, molecule'
an infinite number
of

b *l:::1":Ti:51;ffiJ#,ir"x*,H:"'3::li:T;:"'H"1nd
c Methvlacetv':rlruf#;iT::5[:::ri:fii,T],'5i3;'iranes',each
drru srr "" --
including one ltyorogerr
1 the C_C bond) has
(assuming a rigid-rnol'':ili;liJfi'3i:ff::iilree c
d. 3-chloropropene
no rotation axes ano
ouly one mirror plan(
atoms'

Or crall' a C' tnolecLtle'

 .PzO.llBJeAO .srx€
uorlelor lsrg eqt Surpnlcur seueyd rorrrru o,lu pue (sruees eq1 q8norql sJeqlo eql 'luetu8es
qc?o Jo suorgod .laorreu eq1 q8norql euo) sexe z3 relncrpued.led eerql seq IIeq sruuel V 't
'e4' 'yleroAe 'rJ eq] q8norql Surssed pu€ puoq J-J e
Surprlds qcee'sexe z3 relncrpuafued earqt pue srxe e3 e seq (i11)e1euo;qc(o1e1exo)srrl

''tEe (I|aJF.LO 'eue1d JoJJIU

l€]uozrJoq € pu€
'sexazJ;elncrpued;ed eerql'8uu eql;o eueld eql ol J€lncrpuod:ed srxe ca e seq evrzeJog 'q
.prq.llEJeLO 'Sruol€
g o.a,r1 Surpnlcur qc€o '8uu orll otr Jelncrpuod;ed seueld Jorrrru JnoJ pue 'spuoq elrsoddo
q8no.rqt sexe z3;nog '8uu eql go eueld e8ure,re eql 01 rslncrpuedred saxe z) pue v) s€q 85 .3

.^zJ.lleJeLo
'stuol€ O pue
eql Surpnlcur pue lsJg oql ol Jelncrpuedred reqloue pue 'sruole
J
oqt IIe Surpnycur eueyd rorrur e 'puoq O:J eql qtrr.ryr JeeurlloJ srxe z) e seq epfqepleruroC

'elncelotu zJ e sl1r 's1ueue1e f;leururfs Jeqlo ou qll1yseurJong eql

Surlceuuoc eurl B ol relncrpued;ed pue puoq O-O eql o] J€lncrpued:ed srxe z2 e ser4zgzg

'elncelotu ^tJ e JoJ seueyd do eeJql pue 'srxe tt u :EHN su ,fi1euru,(s orues oql seq O€H 'p

'alncolotu i) e sl 1r os 'sluerueye .{-r1eurur,{s Jeqlo ou s€q lI 'puoq

e8puq lfuaqdrq oqt pue rf, oql q8norqt eueld:or:ru e seq unruo:qclfueqdrqeuezuog 'c

'Jeluec uorsJelur uB puu 'sexe eS pue eg 'saueyd Po eerql pue

^o eeJrll seq osle 'olncelotu qee e Suqeur 'eue1d 'to E pue sexe z3 ;elncrpued.ted
lI I
xrs 's8urr eql o1 Jelncrpuefued sexe zp pue'tJ')
;eeur1loc s€g unruroJqcouozueqrq 'q

'uzJ 'IleJeLo ireluec uorsJelur u€ ssq osl€ ]I 'eue1d Jornu '/o

IJ-e.{-lC oq} o} relncrpuedred 's8uu eql oi lelyered srxe z3 € seq euecoreJoJolqcrp-i I'I 9'n

'elncelotu i) e sl pue 'elncelour er{}Jo eueld rornu eqt fluo seq euelsqlqdeuorolqcrp-7'1 'p

'qzJ 'l1elelo ireluec uorsJenur ue pu€ 'aue1d Jorrnu leluozrJoq

e 'elnceyour eq13o eueld eql o] Jelncrpued:ed srxe z, euo seq eueleqlqdeuoJolqcrp-g'l

'elncoloru nT e U 8un1eu 'seueld Jorrmr o,^d.J

pue 's8uu o,lnl eqi Sururof puoq J-J eql 'srxe zJ euo fluo seq eueleqlqdeuo.rolqcrp-g'1 'q

'elncolotu ryze e
I Surleru '(srxe yedrcur-rd eq] se ueIE] sr c; qcrq,u3to
sselpre8e;) eueld rornu leluozrJoq e pue 'sexe zp relncrpuefued eeql seq aua1uq1du51 'e n'v

'nzJ sI dnor8 lurod ei{J 'tl oi;elncrpuafued

reqlo eql pue 8uu euezueq eqlgo eueld eql euo 'seueld JorIIu o.i.rt pue elnJelour eqlJo
srru 3uo1 eql u.4 op srxe z3 e seq (uor1e1oJ Ieurelur ou Sununsse urzSe) auel'fiecelfueq4

nl '- '.',; T cinorD pue utauiu.(5 ; ralduq3

30 Chapter -l S1'mmetr-r'and Group Theory

{.6 a, Cr clohexane in the chair conformation has a C: axis perpendicular to the average plane
ofthe ring, three perpendicular C2axes between the carbons, and three o, planes, each
including the Cz axis and one of the C2 axes. Ovetall, D3a.

b. Tetrachloroallene has three perpendicular C2 lxes, one collinear with the double bonds,
and the other two at 45o to the CI-C-CI planes. It also has two o', planes, one defined
by each of the Cl-C-Cl groups. Overall, D2a. (Note that the ends of tetrachlorallene are
staggered.)

c. The sulfate ion is tetrahedral. Ta.

d. Most snowflakes have hexagonal symmetry (Figure 4.2), andhave collinear C6, C3 and
Cz axas, six perpendi cular C2 axes, and a horizontal mirror plane. Overall, D61,. (For high
quality images of snowflakes, including some that have different shapes, see K. G.
Libbrecht, Snowflakes, Voyageur Press, Minneapolis, MN, 2008.)

e. Diborane has three perpendicular C2 axes and three perpendicular mirror planes. D2p.

f. 1 ,3,5-tribromobenzene has a Cr axis perpendicular to the plane of the ring, three

perpendicular Cz axes, and a horizontal mirror plane. D31,.

1.2,3-tribromobenzene has a Cz axis through the middle Br and two perpendicular

mirror planes which include this axis. Czu.

1,2,4-trlbromobenzene has only the plane of the ring as a mirror plane. C'.

g. A tetrahedron inscribed in a cube has Tl symmetry (see Figure 4.6).

h. The left and right ends of B:H8 are staggered with respect to each other. There is a
Cz axis through the borons. In addition, there are two planes of symmetry, each
containing four H atoms, and two C2 dxes between these planes and perpendicular to
the original Cz. The point group is Dza.

4.7 A sheet of typing paper has three perpendicular C2 axes and three perpendicular mirror
planes. Overall, D21,.

b. An Erlenmeyer flask has an infinite-fold rotation axis and an infinite number of ou

planes. C.r.

c. A screw has no symmetry operations other than the identity, for a G classification.

d. The number 96 (with the correct type font) has a C2 axis perpendicular to the plane
of the paper, making it C26.

e. Your choice-the list is too long to attempt to answer it here.

f. A pair of eyeglasses has only a vertical mirror plane. C".

g. A 5-pointed star has a C5 axis, five perpendiailar C2 axes, one horizontal and five
vertical mirror planes. D57;.
 .p
'1€O :sOS

t1 :sgt4 asq :t91.3 ^zJ :t{OS

.c

^23 :z13zg3
,/ :9ds J ^€J :elJd
.q

qre :rl,zoe)( ^zJ iglJl

.o
^sJ :€IJOA
.u :t€'g tuelqord 'e ll.v
('lJ EurlseJelul ssel qcnu e sl dno;E lulod eql pue ',ft1eurur,{s
ou sr ererll'pepnlcur sr eAIeA pe{ooJc eq}JI)'pepueruuroceJ sI leeglr\ e1c.{crq IBnlcB ue Eutruesqo
llueruu8rsse dnor8 lurod aql lceJJe u€c ssoJc se>1ods eql qclq,& ur s.,{eltr lueJeJJIp pue 'elqtssod ere
slueure8uerre Jeqlo 'p8O sl dnorS lurod eql'lueruqcegego epIS Jleql ol lcedser qlla elellJelle srred
eqlJl 'rulr eqt rlllli\ tceuuoc (qnq eqlgo {cuq pu€ }uor; eql q}oq o} peqcupe) selodsgo srred eq}
,l\oq uo spuedep lueuruErsse dnor8 ]urod eq1 'selods T,Esequ^\oqs Ieaq^\ eqJ, :leeq^\ elc,(clg

'C :V x S zJ :€ x € nzJ :9 x9 :seoultuoq ^rP :rerrro;1a;;tg

ne3 :runlruoly rzq :11eqeseg z3 :(sumq lecqueplgo) spuzH 0l'?
t3 't nz)

tteo .I tC 'p

nt) 'q 'J 'c

.3 qvo 'q
(suorlerocep SuFouBt) ^@3

qte 'v
(se1oq elou) )
6'n

nt) 't n9J 'o

q*e .I nz) 'p

nBc 'q 'J 'c

qz) -a (sqqq rnoJ eql elou) qn1 'q

t3 qze 'e
8't
'{@O (llBJeAO 'eue1d JoJrIIu leluozlJor{ e pue 'seuzld rorrtur noSo requrnu
elrugu u€ 'sexe zp relnctpued-red;o Jeqlunu elrugut ue 'sxe -p 3 seq JeI{s€Al le}eru V 't
'Il ',llluepl sql uerll Jeqlo uorlsJedo ,{leurur,$ ou wq >1oog urelde3 '!

') 'aue1d rorrru e ,(1uo seg {JoJ V 'q

,{roeql dno.rg pue,{4euurfg p relduq3

32 Chapter 4 Symmetry and Group Theory

b. Problem 3.35: a. PH:: G" e. IFs: C+" h. SnClz: O"

b. HzSe: Cz" f. XeO:: Cr" i. KrFz: D-r,

c. SeF+: O" g. BF2CI: C2" j. IO2F52-: D51,

d. PFs: D:r,

4.12 Figure 3.8: a. CO2: Dap d. PCls:D:r, f. IFt Dsn

b. SO::D:a e. SFe: Or g. TaFs3-'. Da6

c. CH+: Ta

b. Figure 3.15: a.CO2: D*p e. SNF:: C:u i. SOF+: Cz"

b. COFz: Cz" f. SOzClz: O" i.ClOzFz: Cz,

c. NO2 : C2" g. XeO:: G" k. XeOgFz:D:r'

d. SO:: D:r, h. SO+2-: Za l.IOFs: C+"

4.13 a. p, has Coy slmmetry. (Ignoring the difference in sign between the two lobes, the point
group would be D*1,.)

b. d,rhas D211sJmmetry. (Ignoring the signs, the point group would be D+n.)

c. d,-r,hasD21 slmmetry. (Ignoring the signs, the point group would be Da1.)

d. d"rhas Do7, slmmetr!.

e. f,y"has Z7 slmmetrY.

4.14 a. The superimposed octahedron and cube

show the matching symmetry elements.

The descriptions below are for the cz, Co

elements of a cube: each element also
applies to the octahedron.

E Every object has an identity

operation.

8 C3 Diagonals through opposite

comers of the cube are c3 axes.

6 Cz Lines bisecting opposite edges are C2 axes.

6 Cq Lines through the centers of opposite faces are Cq a-xes. Although there are only
three such lines, there are six axes, counting the Ca' operations.
 qsc 'o
qzc 't
qve 'p
qbe 'q
nzJ .J
qze .3
nzJ 'q
nzJ
T
qze 'a
9r'n
13 reqclrd .3

.J
(1'7 ern8tg ees)rzg ll?qeseq

nzJ e1e1d eruoq 'a

"*c l€q 'p

'J dec 'c

qze xoq scJeil€q 'q

,t*c[ elcJrc {cep-uo 'e gr'v

.J
o
aO 'q

'se8pe elrsoddo o4 q8norqt are seueld JorIIIu eseqJ ps9

'eqnc eqlJo seceJ eq] o1 1e11ered are seueld JoJrIIu eseqJ 'tsE

eql
'saxe eS osle eJ? sexe ep eS8

'sexe ts osl€ aJ? sexe rp eql tS9

'Jeluec uorsJe^ur eql sr eqnc eqlJo Jetruec eql !

.sexezJ
s€ IIe^\ se sexe vC era seceg elrsoddo;o sreluec eql q8norql seu{ eqJCrJ:) zC t,

t€ ,&oeq1 dnorg pue,fi1eunuf,g 7 ;e1duq3

 Chapter 4 Symmetry and GrouP Theory

v
N A
F2 l

ill \lN-F,
4.17 SNF3 u'7'\,
F'
/
F3 (top view)
+> x

Symmetry Operations
D Fl F3

N-F: N-Fj
N-Fr /
/ n
F^
.J F2 L2

after E after C3 after o,(xz)

Matrix Representations (reducible)

E
cos
2n 2n 1 1/J (,
ool ^{1 2 L
[1 o o"l
[r
u:lo t ol c{
a* '')* E
.VJ 1^
sln- cos- l0 -1 0
. Lll Ltt
u 4
U o"(xz):
z L |

10011 1001"l
001 0 01

Characters of Matrix Representations

a
J

Block Diagonalized Matrices

Ia
1|lJ |^
I

r;?l:l
p o tlll
)l
'l
I
)l
-)
t^
IU it
100
I 'l0l
I1I
0[1

Ineducible Representations

E 2 Ct 3 o, Coordinates used
2 -l 0 (x,Y)
1

Character Table

Ct,l E 2Cz 3ou Functions

11 z ,
,|
.fl2 1 -l R"
E -l 0 (-lr,.y), (R.,, R,) @'-f,xy)(xz,yz)
 o:Ix(t-)+(i-)xt+
I x I +(t-) x (t-)+(t-) x I + I x (t-)+(t-) x (t-)+ I x I :zJ x IJ

ntg Suu4clew
I I I- I_ I_ I_ II e1
nzg Surqclew
I l- I I- I- I I_ I z1
n€Br
8ulqcl€tu T-
I I I I- I I- I- I tg 'p

I00 I00
0t0 0t-0
00I- :(zt)o 00r :(40

r-00 I-00 r-00

0t0 0r-0 0I-0
00r :Qk)o 00t- 00i :(x)zJ

I-00 I00 I00

0I0 0t-0 0I0
00r- :(azc 00t- :(z)73 00r :T
'q

HH
\/'J:i 'suotleredo (zrt)o

HH \-
-/ pue'(zx)a'({x)o '!'(x)zJ '(AzJ 'Q)O 'g e^eqselncolou ryzcr
6T''

leuo8oquoere,(eqtSutnord'O:(t-) X I +(t-) x (t-)+ I X (I-)+ I X I

:'y pue 'g 3ur,{1dt11n61 'p

'nY+ ngZ:
J sI Ielol eqJ

stuercgJeoc z eql tuo4l i- I- I I 'y

sluercrJJeoc [pue x eql rxog I I- I- I 'g
(qo)x (t)x (rdx (q)x
'elqel eql uI ulroqs suotlelueserder
eql qlr.ry\'sect4etu IXI eeJql olul pezll€uo8erp lcoyq eq u€c secIJlBIu eseqJ 'c

r-0 0 i-0 0 I00 I00

0r0 0 I-0 0 t-0 0 t 0
00I:no 0 0 I-:1 0 0 I-:T 0 0 r:E 'q

IJH
\/ 'suorle;edo '!'z)'g 'E 8I't
J:J '1o pue eneq selnceloutqzJ
/\
HIJ
sg ,ftoeq; dno;g pue,{.l1eruru,(5 p relduq3
36 Chapter 4 Symmetry and Group Theory

f1 X f3:1 x 1+(-1) x 1 +(-1) x (-1)+1 x (-1)+(-1) x (-1)+ 1 x (-1)

+ 1 x I +(-1) x l:0

x 1 +(-l) x I +l x (-1)+(-l) x (-1)+(-1) x (-1)+1 x (-1)

fz X f::l
+(-1)x1+1x1:0
4.20 &: 8 (the total number of symmetry operations)

b. Atx E:1 2+2x 1 X 0+1 X (-2)+2X I x 0+2x 1 X 0:0

X
A2xE:1x 2+2x 1x 0+1 x (-2)+2x (-1) x 0+2x (-1) x 0:0
Btx E:1 x 2+2x (-1) x 0+1 x (-2)+2x 1x 0+2 x (-1) x 0:0
Bzx E:1 x 2+2 x(-1) x 0+1 x eD+2 x (-1) x 0+2x I X 0:0

c. E:4+2x0+4+2 X 0+2 X 0:8

AiI-r2x1+7+2 X 1+2X 1:8
Az:1*2XI+l+2 X 1+2X 1:8
Br:1+2xl+I+2 X l+2XI:8
Bz:I+2xl+l+2 X 1+2X 1:8

d. l=2Ara Bt+ 82+ E:

A;ll8l1 x 6+2 x I x 0+ | x 2+2 x I x2+2 x I x 2l:2
Az:ll8ll x 6+2 x I x 0+ | x 2+2x (-1) x 2+2 x (-1) x 2l:0
,Br: 1/8[1 x 6+2 x (-l) x 0+ | x 2+2 x I x 2+2 x (-1) x 2]: 1

Bz:1l8ll x 6+2 x (-1) x 0+ 1x 2+2x (-1) x 2+2x 1x 2l:l

E: 11812 x 6+2 x 0 x 0+ (-2) x 2+2 x 0 x 2+2 x 0 x 2l: 1

lz:3 At+2Az+ Bi
A;ll8ll x6+2xIx4+ 1 x6+2xlx2+2x 1x0l:3
Az:ll8ll x6+2xl x4+l x6+2x (-1)x2+2x (-1)x0):2
Br: 1/8[1 x 6+2 x (-1) x 4+1 x 6+2 x I x 2+2 x(-1) x 0]: I
Bz:1l8ll x 6+2x (-Dx 4+ I x 6+2x (-1) x 2+2x 1 x 0l:0
E: Il8l2 x 6+2 x 0 x 4+(-2) x 6+2x 0x2+2 x 0 x 0l:0
4.21 Cz,
f r3At* A2* E:
A;11617 x 6+2x I x 3+3 x 1 x2l:3
Az:ll6ll x 6+ 2 x I x 3+3 x (-1) x 2l: I
E: 116[2 x 6+2 x (-1) x 3+3 x 0 x2]:I

lz: Az* E:
Alll6ll x s+2x I x (-1)+3 x 1 x (-1)l:0
Az:11611 x s+ 2 x I x (-1)+3 x (-l) x (-1)l: I
E: 11612 x 5 + 2 x (-r) x (-l)+3 x 0 x (-1)l:2
roq-{s arc.{ra, :8.? rooH ur,rd€r,^.,rrtfii'.t"#:ff0::'?[Hi,3]'fr?3ul#'",,','lli Ez.i

I_ + Ps
$ Pg

+ no
t- a no

+ s 4s

I_ + os
{-'p
I* a 75'

*p
+ s
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r-)
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TJ
+ ,b a Z;

+ zc I{ s zJ
+
,(

I_ + n)
I_ a v)

+ s
X ,nfp *p

'uo4elueserder 'uo4eluesardsl azg eql ur

3r€r eqlJo esoql qcl€ru sJelc"J€qc zt-xp olq.l" sJelcuJeqc eq] qcluru sJolceJeqJ "p eq1'

o :
[zt - zt + 0 + 0 + 0 + 9 - zr - 0 + 0 + 8 I ]8t lr '.'zJ
t:Lzt + zr + 0 + 0 + 0 + 9 - zr + 0 + 0 + SIl8ttt;'U
0:[0 +tz- 0+0+ 0+T,r +0+0 +0+zr]8vlr ''g
o :lzr + zr -0 + 0 + 0 + 9 + zr * 0 + 0 + gl}vlr .'zY
0 :lzr - T,r -0 + 0 + 0 + 9 + T,t + 0 + 0 + 9l8vlr ;'-tv
o :lzt + zr -0 + 0 + 0 + 9 - zr - 0 + 0 + 8tl8ilt J-zJ
o :lzt - (l -0 + 0 + 0 + 9 - T,r + 0+ 0 + 8ll8t/t :'rJ
t : [o + rz+ 0+0 +0 +zr +0 + 0 + o + zilw.t']z
o :[T,r - zr +o + o + o + 9 + zr - o + o + 9l8rlt ::Y
r :lT,r + T,t +0 + 0 + 0 + 9 + zr + 0 + 0 + 9f8vtr :dtv
:',J +"7 +otV:LJ
tto

,{.roeq1 dno:g pue f:1aruru,{g 7 raldeq3