MODULEI

V
I
ntr
oduct
ion

Themol ecularspect roscopyisthestudyoft heinteracti

onofel ectromagnet i
cwav es
andmat t
er.Thescat teringofsun’sraysbyrai
ndropstopr oducear ainbowandappear ance of
acolorfulspectrum whenanar r
owbeam ofsunlighti
spassedt hroughat r
iangularglasspr i
sm
arethesi mpleexampl eswher ewhiteli
ghtisseparatedintot hev isibl
espect r
um ofpr imary
colors.Thisvisibl
elighti smer el
yapar tofthewhol espectrum ofel ectromagnet icradiati
on,
extending fr
om t he r adio waves to cosmicrays.Al lt
hese appar entlydi ff
erentf orms of
el
ectromagnet icradiationst r
avelatthesamev el
ocit
ybutchar acterist
icallydifferfrom each
otherintermsoff requenci esandwav el
ength(
Table1).

Thepropagationoft heseradi
ati
onsinvol
vesbothelectr
icandmagneticforceswhich
giv
er i
setot heircommoncl assnameel ectr
omagneti
cr adi
ati
on.Inspectr
oscopy,onlythe
eff
ectsassociat
edwi thelectr
iccomponentofelect
romagneti
cwav eareimport
ant.Ther
efore,
theli
ghtwav etravel
i
ngt hroughspaceisrepresent
edbyasi nusoidalt
race(f
igur
e1) .I
nt hi
s
di
agram λi
sthewav el
engthanddistanceAisknownast hemaxi mum ampl
itudeofthewave.
Al
thoughawaveisfrequentl
ycharacter
izedi
nter
msofi tswavelengt
hλ,oft
ent het
ermssuch
aswavenumber,
frequency(ν)
,cycl
espersecond(cps)orher
tz(Hz)areal
soused.

Fi
gur
e1:
Wav
eli
kepr
opagat
ionofl
i
ght(λ=wav
elengt
h,A=ampl
i
tude)

Theunitcommonl yusedt odescr i

bethewav el
engthi scentimeters( cm),thediff
erent
unit
sareusedt oexpressthewav el
engthsindif
ferentpartsoft heel
ectromagnet icspectr
um.
Forexample,
intheultrav
ioletandv i
sibl
eregi
on,theunitsusear eangstr
om ( Ǻ)andnanomet er
-1
(nm).Intheinfr
aredregion,thecommonl yuseduni tiswav enumber(cm ) ,whichgivest he
numberofwav espercent i
met er
.Thef ourquanti
ti
eswav elength,wavenumber ,frequencyand
vel
ocit
ycanber el
atedtoeachot herbyfoll
owingrel
ationships:

Emi
ssi
onandAbsor
pti
onspect
roscopy
Whenener gyintheform ofli
ght,heat ,orchemicalagentsi sgiv ent oanel ement ,the
electronsofitsat omsacceptt heener gyandgot ohi gherener gyl evels.Howev er
,t hese
electronshavetoemi tener
gyinordertor eturntothei
rgroundst ate,sincet heexcitedst ateis
unstable.Thef r
equenciesofli
ghtemi tt
edi nsuchacaseconst i
tutet he emissionspect r
um
(Figure2).Whenanel ectr
oncomesdownf rom anexcit
edst at
etot hegr oundst ate,itemi t
sa
phot onofenergy.Theener gyofthisphot ondependsont hediff
er encebet weent heener gy
l
ev elsoftheexci
tedstateandgroundstateoft hatel
ectr
on.
Fi
gur
e2:ConceptofEmi
ssi
onspect
rum

Thei ntensi
tyoftheli
ghtemitt
ed(atthespecif
icfr
equencycorrespondi
ngtotheener
gy
l
eveldi
ff
erence)isproport
ionalt
oconcentr
ationoftheanaly
te.Spect
roscopicst
udi
esbasedof
t
hisemitt
edl i
ghtisknownasemi ssi
onspectr
oscopy.

Flameemi ssi
onspectr
oscopyorFlamephot ometr
yisacommonexampl eofappli
cati
on
ofemi ssionspectroscopy
.Howev er,Fl
ameemi ssi
onspectroscopyi
sli
mit
edonlytoalkal
iand
alkal
ineear t
hel ementsastheionizati
onener
gyofonl ytheseelement
sarel
ow enoughtobe
thermallyexcit
edt oyi
eldaemissi
onspectrum (
Figure3)
.

Fi
gur
e3:
Flameemi
ssi
onspect
roscopyorFl
amephot
omet
ry

I
nduct
ivelyCoupledPlasma–At omicemi ssi
onspectroscopy( I
CP-AES)spectr
oscopyis
asuperi
orexampl ethati
nvolvesinj
ect
ionofthesampl ei nt
ot heplasma,resul
tingi
nemission
spect
rum f
orallelementspresentandsubsequently
,thei
rest
imat i
on(Figur
e4) .

Al
thougheachel ementemitsenergyatmul ti
plewav el
engt hs,i
ntheI CP-AEStechniqueit
i
smostcommont oselectasingl
ewav elength(orav eryfew)foragi venelement .Theintensit
y
oftheener gyemit
tedatt hechosenwav elengt
hispr oport
ionaltot heamount( concentr
ation)of
thatelementinthesampl ebeinganaly
zed.Thus, bydeterminingwhi chwav elengt
hsareemi t
ted
byasampl eandbydet ermini
ngtheiri
ntensiti
es,theanalystcanqual it
ati
velyandquant it
ativel
y
fi
ndt heel
ement sfrom thegiv
ensampl erelati
vetoar efer
encest andard.
 Fi
gur
e4:
Induct
ivel
yCoupl
edPl
asmaAt
omi
cEmi
ssi
onSpect
roscopy(
ICP-
AES)

Elect
ronsofanelementwhichareinthegroundstatemayabsorbinci
dentenergyin
ordertor each a hi
gherener
gyst at
e.The fr
equencies ofl
i
ghttransmit
ted t
hrough t
his
substance,wit
hdarkbandsshowi
ngabsorbedli
ght,const
it
utet
he 
absorpt
ionspectr
um ofthe
substance.

Fi
gur
e5:
TheconceptofAbsor
pti
onspect
roscopy

The spect
roscopi
cstudiesbased on ‘
absorbance’ofli
ghtatconcer
ned f
requency
(
cor
respondi
ngtotheenergygap)i
scall
edabsorpt
ionspectr
oscopy(
Figur
e5)
.

Al
lty
pesofspect
roscopydi
scussedher
onar
eabsor
pti
onspect
roscopy
.

Lamber
t–Beer
’sl
aw
Lambert'
slaw st
ated t
hatabsorbanceofa mat eri
alsamplei sdirect
lypr opor
ti
onaltoits
thi
ckness(pathlengt
h).Muchl ater,August 
Beer
 di
scoveredanotherattenuati
onrelat
ionin
1852. 
Beer'
slaw 
stat
edthatabsorbanceispropor
ti
onaltotheconcentr
ati
onsoft heatt
enuat
ing
speci
esinthemateri
alsample.
Combi
nati
onofthesetwolawsresul
tedinLambert–beer
’slaw,whichstat
esthatabsorbance
ofamonochr
omat i
cli
ghtpassi
ngthr
oughamedi um i
sproporti
onaltoboththi
ckness(
l)ofthe
medi
um aswel
lastheconcentr
ati
on(c)oft
heabsorbi
ngspecies.

Mat
hemat
ical
l
y,

Fi
gur
e6:
ConceptofLamber
t-
Beer
’sLaw

Li
mit
ati
onsofLamber
t–Beer
’sl
aw

Theli
near
it
yoftheBeer
-Lamber
tlawi
sli
mit
edbychemi
cal
andi
nst
rument
alf
act
ors.Causesof
nonl
i
neari
tyincl
ude:

 devi
ati
onsi
nabsor
pti
vi
tycoef
fi
cient
sathi
ghconcent
rat
ions(
>0.
01M)duet
o
el
ectrostati
cinteracti
onsbet weenmol eculesincl
osepr oxi
mity
 scatt
eringoflightduet opar ticulatesinthesample
 fl
uoresecenceorphosphor escenceoft hesample
 changesi nrefr
activeindexathi ghanal yt
econcentrati
on
 shif
tsinchemi cal equil
ibri
aasaf uncti
onofconcent r
ati
on
 non-monochr omat icradiat
ion, dev i
ati
onscanbemi ni
mi zedbyusingarel
ati
vel
yfl
atpar
t
oftheabsor pti
onspect rum suchast hemaxi mum ofanabsor pt
ionband
 str
aylight

UV–VI
SSpect
roscopy
Thi
sabsor ptionspectr
oscopyusesel ectromagnet i
cradi
at i
onsbet ween190nm t o800
nm andisdivi
dedi ntotheult
ravi
olet(UV,190-400nm)andv i
sible(VIS,400-800nm)r egions.
Si
ncet heabsorptionoful t
raviol
etorv isi
bleradiat
ionbyamol ecul
el eadst r
ansi
ti
onamong
el
ectr
onicenergylev elsoft
hemol ecule,iti
salsoof tencall
edasel ectroni
cspectroscopy.The
i
nfor
mat i
onprov i
dedbyt hi
sspect roscopywhencombi nedwitht heinformationprovi
dedby
NMR and I R spect raldat
al eads tov al
uable struct
uralproposals.Nat ure ofElectronic
Transiti
onsThet otalener gyofamol eculei sthesum ofi t
selectroni c,it
sv i
brati
onalenergyand
i
tsr otati
onalener gy.Ener gyabsor bedi nt heUV r egionpr oduceschangesi ntheelectroni
c
energyoft hemol ecule.Asamol eculeabsor bsener gy,anel ect r
oni spr omotedf rom an
occupiedmol ecularor bital(usuall
yanon- bondingnorbondi ngπor bit
al)toanunoccupi ed
molecularor bital(anant i
bondingπ∗orσ*or bi
tal
)ofgr eaterpot enti
alener gy(fi
gure3).For
mostmol ecules,thel owest -energyoccupi edmol ecul arorbi
talsareσor bit
als,whi
chcorrespond
toσbonds.Theπor bitalsli
eatr elati
v elyhigherener gylevelst hanσor bit
alsandt henon-
bonding or bi
talst hathol d unshared pai rs ofel ectrons lie ev en athi gherenergi
es.The
anti
bondi ngor bit
als( π*andσ*)ar eor bitalsofhighestener gy.Ther elat
ivepotenti
alenergi
es
oftheseor bit
alsandv aiouspossi bl
et r
ansi ti
onshav ebeendepi ctedi nf i
gure7.

Fi
gur
e7:Relati
veener
giesofor
bit
alsmostcommonl
yinv
olv
edi
nel
ect
roni
cspect
roscopyof
or
gani
cmolecul
es

Thesat ur
atedali
phat i
chy drocarbons(alkanes)exhi bi
tonlyσ σ*t r
ansiti
onsbutdependi ngon
thef unct
ionalgroupst heor ganicmol eculesmayunder gosev eralpossiblet r
ansiti
onswhi ch
*canbepl acedinthei ncreasi
ngor deroft heirenergi
esviz.n π*<n σ*<π π*<σ π*
<σ σ*.Si nceallthesetransit
ionsrequiref i
xedamountofener gy( quantized),anultr
av i
oletor
visi
blespect r
um ofacompoundwoul dconsi stofoneormor ewel ldef i
nedpeaks,each
corresponding t
ot het r
ansferofan el ectron from oneel ectr
onicl evelt o another.Ift he
diff
erencesbetweenel ectronicenergylevel soft woelect
ronicstatesar ewelldefinedi.e.ifthe
nucleiofthetwoat omsofadi atomi cmol eculear ehel
dinf i
xedposition,t
hepeaksaccor dingly
shouldbeshar p.However,vi
brati
onsandr ot
ati
onsofnucleioccurconst
ant
lyandasar esul
t
eachel ect
ronicstat
einamol ecul
ei sassoci
atedwi t
hal argenumberofv ibr
ati
onaland
rotati
onalstat
es.Atroom temper at
ure,t
hemoleculesinthegroundstat
ewillbeinthezero
vibrat
ional
level(
Gυo)
.Thisisshownschemat i
cal
lyinfi
gure8.

Fi
gur
e8:Ener
gylevel
diagram showi
ngexci
tat
ionbet
weendi
ff
erentv
ibr
ati
onal
andr
otat
ional
l
evel
soft
woelectr
onicstates

Thet ransit
ionofanel ectronf r
om oneener gylevelt oanot herist husaccompani edby
simultaneous change i nv ibr
ati
onaland r otati
onalst ates and causes t ransi
ti
ons bet ween
vari
ousv i
brationalandr otati
onallev elsofl owerandhi gherener gyelectr
oni cstat
es.Ther efore
manyr adiat
ionsofcl oselyplacedf r equenci esar eabsor bedandabr oadabsor ptionbandi s
obtained.When a mol ecule absor bs ul traviol
etorv i
siblel ightofa def i
ned energy ,an
assumpt ioni smadet hatonlyoneel ectroni sexcitedf or m bondi ngor bit
alornon- bondi ng
orbi
talt oanant i
-bondingor bit
alandal lot herelectr
onsr emai nunaf f
ected.Theexci tedst ate
thuspr oducedi sf ormedi nav eryshor ttimei .e.oftheor derof10- 15seconds.I naccor dance
withFr anck-Condonpr inci
ple,duringel ectronicexcitati
ont heat omsoft hemol ecul
edonot
mov e.Themostpr obablet r
ansit
ionwoul dappeart oinvolv et hepromot i
onofoneel ectr
onf rom
thehi ghestoccupi edmol ecularor bital( HOMO)t othel owestunoccupi edmol ecularor bital
(LUMO) ,butinmanycasessev eraltransi t
ionscanbeobser v ed,givi
ngsev eralabsorpti
onbands
i
nt hespect rum.Wecanhav eagener alv iew ofthepossi bletransiti
onspr evail
i
ngi nor ganic
compounds.
Alkanescanonl yundergoσ σ*t r
ansit
ions.Thesear ehigh-ener gyt ransitionsandi nvolvevery
shor twav elengt hultr
avioletlight(<150nm) .Theset ransit i
onsusual lyf allout-sidethegener all
y
av ailabl emeasur abler angeofUV- visi
blespect r
ophot omet er s( 200- 1000nm) .Theσ σ*
transi tionsofmet haneandet hanear eat122and135nm, respect ively.Inal kenesamongstt he
av ailabl eσ σ*andπ π*t ransit
ions,theπ π*t ransiti
onsar eofl owestener gyandabsor b
radi ationsbet ween170- 190nm.I nsat urat edal i
phat icket onest hel owestener gyt ransit
ion
i
nv olvest het ransf erofoneel ectronofthenonbondi ngel ectronsofoxy gent ot herelati
velylow-
l
y ingπ*ant i
-bondi ngorbital.Thisn π*t ransitionisofl owestener gy( ~280nm)buti sofl ow
i
nt ensi tyasi ti ssy mmet ryf orbidden.Twoot herav ailabl
et ransi tionsar en π*andπ π* .
Themosti ntensebandf orthesecompoundsi salway sduet oπ π*t r
ansition.Inconj ugated
dienest heπ π*or bital
soft hetwoal kenegr oupscombi net of orm new or bital
s– t wo
bondi ngor bitalsnamedasπ1andπ2andt woant i
bondi ngor bi talsnamedasπ3*andπ4* .I
tis
appar entt hatanew π π*t r
ansiti
onofl ow ener gyi sav ailabl easar esultofconj ugati
on.
Conj ugat eddi enesasar esultabsor batr elativelylongerwav elengt ht handoi sol
atedal kenes
(seef igure10) .

Spect
ral
Measur
ement
s

TheUV- Visspectraareusual l
ymeasur edi
nv erydil
utesoluti
onsandt hemosti mport
ant
cri
teri
onint hechoiceofsolventisthatt
hesol
ventmustbet ranspar
entwithi
nthewavel
ength
rangebeingexami ned.Tabl
e2l i
stssomecommonsol ventswiththei
rlowerwavel
engt
hcutoff
l
imits.Belowt heseli
mits,t
hesolventsshowexcessi
veabsorbanceandshouldnotbeusedt o
determineUVspect rum ofasample.

Sol
ventEf
fect
s

Hi ghl
ypur e,non- polarsol ventssuchassat urat
edhy drocarbonsdonoti nt
eractwi th
solutemol ecul
esei theri nt hegr oundorexci t
edst at
eandt heabsor pt i
onspect rum ofa
compoundi nt hesesol ventsi ssimi l
art otheonei napur egaseousst ate.Howev er,polar
solventssuchaswat er,alcohol set c.mayst abili
zeordest abil
izethemol ecularorbitalsofa
mol eculeei t
herint hegr oundst ateori nexcit
edst ateandt hespect r
um ofacompoundi nthese
solventsmaysi gnifi
cant lyv aryf r
om t heoner ecordedi nahy drocarbonsol vent.(
i)π π*
TransitionsI ncaseofπ π*t r
ansi t
ions,theexcitedst atesar emor epol arthanthegr ound
stateandt hedipol e-
di poleint er
actionswi thsolventmol eculeslowert heener gyoftheexci ted
statemor ethant hatoft hegr oundst ate.Thereforeapolarsol ventdecreasest heenergyofπ
π*t ransit
ionandabsor ptionmaxi mum appear s~10- 20nm r edshift
edi ngoi ngfrom hex aneto
ethanol solvent
.
 Tabl
e2:

(i
i)n π*Tr ansi
ti
onsIncaseofn π*t ransi
ti
ons,t
hepolarsolvent
sform hydrogenbonds
withthegroundstateofpolarmoleculesmorereadi
lythanwit
htheirexci
tedst
ates.Therefor
e,
i
npol arsolv
entstheenergi
esofel ect
roni
ct r
ansi
ti
onsareincr
eased.Forexample,thefi
gure9
showst hattheabsor
pti
onmaxi mum ofacetoneinhexaneappearsat279nm whi chinwateris
shif
tedto264nm, wi
thablueshif
tof15nm.
Fi
gur
e9:
UV-
spect
raofacet
onei
nhexaneandi
nwat
er

Somei
mpor
tantt
ermsanddef
ini
ti
ons

(i)Chromophore:Theenergyofradiat
ionbei ngabsor beddur i
ngexcitati
onofel ect
ronsfrom
groundstat
etoexcitedstat
epri
marilydependsont henucl eithathol
dt heelect
ronstogetherin
abond.Thegr oupofat omscont ai
ningelectronsr esponsiblefort heabsorptioniscalled
chromophore.Mostoft he si
mple un-conj
ugat ed chromophor es gi
v erise t
o high energy
tr
ansit
ionsofl
it
tleuse.Someofthesetransit
ionshavebeenl istedintable3.

Tabl
e3:
 Forexampl e,alkanescont ai
nonlysinglebondswi t
honl ypossibleσσ*t ypeelectronic
transiti
ons. These t ransiti
ons absor b radiati
ons shor t
er t han wav el
engt
hs t hat are
exper i
ment all
yaccessibleinusuallyavai
labl
espect rophotomet er
s.Insat ur
atedmoleculeswi t
h
het er
oatom bearingnon- bondingpairsofelectr
ons,nσ*t ransit
ionsbecomeav ail
able.These
areal sohighenergytransiti
ons.Inunsaturat
edcompounds, ππ*t ransiti
onsbecomepossi bl
e.
Alkenesandal kynesabsor b~170nm butt hepr esenceofsubst i
tuentssigni
fi
cantl
yaf fects
theirposition.Thecar bony lcompoundsandi mi nescanal sounder gonπ*t ransit
ionsin
addi t
iontoππ* .Amongstt hese,t
hemostst udiedtransit
ionsar enπ*ast heseabsor bat
relati
velyl
ongerwav elength280- 300nm.Thesear el owintensit
y(ε10- 100)tr
ansi
ti
ons.

(i
i)Auxochr
ome:Thesubst i
tuentsthatthemselv
esdonotabsorbult
ravi
oletr
adi
ati
onsbutthei
r
presenceshif
tstheabsorpti
onmaxi mum t olongerwav
elengthar
ecal l
edauxochromes.The
substi
tuent
slikemethyl
,hy droxyl
,alkoxy,hal
ogen,ami
nogr oupetc.aresomeexampl esof
auxochromes.

(
ii
i)Bathochr
omi c Shi
ftorRed shi
ft
:A shi
ftofan absor
pti
on maxi
mum t
owar
ds l
onger
wavel
engthorlowerenergy
.

(i
v)Hy psochr
omi cShiftorBl
ueShi
ft
:A shi
ftofanabsor
pti
onmaxi
mum t
owar
dsshor
ter
wavel
engthorhigherenergy
.

(
v) Hypochr
omi
c Effect
:An ef f
ectt hatresult
si n decr
eased absorpt
ion i
ntensi
ty.(
vi)
Hyper
chromi
cEf
fect
:Anef f
ectt
hatresul
tsi
nincreasedabsor
pti
onint
ensit
y.

Appl
i
cat
ionsofEl
ect
roni
cSpect
roscopyi
nPr
edi
cti
ngAbsor
pti
onMaxi
maofOr
gani
cMol
ecul
es

1:
Conj
ugat
edDi
enes,
Tri
enesandPol
yenes

Thepr esenceofconj ugatedoubl ebond decreasest heener gydiff

erencebet ween
HOMO andLUMO ofr esulti
ngdi ene.Thef igure10showst hechangei nenergyofMO on
conjugation.Asar esult,t
her adiat
ionsoflongerwav el
engthareabsor bed.Theconj ugationnot
onlyr esult
si nbat hochromicshi ft(longerwav el
ength)butal so i
ncreasesthei ntensityof
absorption.Ast henumberofconj ugateddoublebondsisi ncreased,thegapbet weenhi ghest
occupied mol ecularor bi
tal( HOMO)and l owestunoccupi ed mol ecularorbit
al( LUMO)i s
progressivel
ylower ed.Therefore,t
hei ncr
easeinsizeoftheconj ugat
edsy st
em graduallyshifts
theabsor pti
onmaxi mum ( λmax)t olongerwav el
engthandal soi ncr
easest heabsorption.For
example,et
hyl
eneabsor
bsat175nm (ε=1000)andtheconj
ugati
oninbut
adi
enegi
vesast
rong
absor
ptionatl
ongerwavel
engt
hat230nm andwithhi
gheri
ntensi
ty(
ε=>1000).

Fi
gur
e10:
Eff
ectofconj
ugat
iononor
bit
als’
ener
gyandr
espect
iveπ-
π*t
ransi
ti
on

Thepr esenceofal kylsubsti

tuent
sondoubl ebondal sopr oducesbathochromicshi f
t
andhyperchr omi ceffect.Theseef f
ectsareadditi
veindienesandupt osomeext entintr
ienes.
Theopenchai ndi enescanachi eves-ci
sors-transconf or
mat i
onsandsi mil
arlydienesystem
can be homoannul arorhet er
oannularin cycli
c systems.I n 1941,Woodwar d suggest ed
empiri
calrulesf orpredicti
ngt heabsorpti
onofopenchai nandsi x-
member edringdieneswhi ch
havebeenl ateronext endedt olargenumberofdi enesandtrienes(Table4).

Tabl
e4:
 Forexampl
e,her
etheabsorpti
onmaximafordienes1and2havebeencal
cul
ated
accor
dingtoWoodwardrul
es.Thecomparisonofcal
culatedλmaxv
alueswi
thobser
vedλmax
val
ueshighli
ght
stheimpor
tanceoftheser
ules.
 Ast henumberofdoublebondsi nconjugationincr
eases,thebathochr
omic( t
owards
l
ongerwav elengt
h)shif
tinlowestener gyabsor pti
onmaxi mai sobserved.Theincreasein
conjugationgradual
l
yshift
sthemaximat ovisi
bleregion(>400nm)andi mpart
scolourtothe
sampl e.Table5showstheλmaxshi f
tinMe( CH=CH) nMewi t
hincreasingnumberofconjugat
ed
doublebonds.β-Car ot
ene(fi
gure11)responsibl
ef orredcol
orincarrotsi
satypi
calexampleof
poly
enewi t
h11conjugateddoubl
ebondsandexhi bit
sλmaxat445nm.

Fi
gur
e11:St
ruct
ureofβ-
car
otene

Tabl
e5:
 2:
Car
bony
lCompounds

Car
bony lcompoundshav et wopr i
ncipalUVr adiat
ions,theallowedππ*t r
ansiti
ons
andt heforbi
ddennπ*t r
ansiti
ons.I nami des,aci ds,estersoraci dhali
des,thesubstit
uents
viz.NR2,OH,OR, or–Xoncar bony lgr oupshowpr onouncedhy psochromiceff
ectont henπ*
transi
ti
ons.Thehy psochromi cef fecti sduet oi nduct iv
eef fectofnitr
ogen,oxygenorhal ogen
atoms.Thehet eroat om withdrawsel ectronsfrom car bony lcarbonandmakescar bonyloxygen
l
onepai rofelectr
onsmor estabil
izedduet oitsinvolvementi ni
ncreasingC=Obondor der.Asa
result
,then π*t ransit
ionoft hesecompoundsi sshi f
tedt o200-215nm rangerelati
veto270
nm inaldehydesandket ones.Conj ugationoft hecar bony lgroupwi t
hdoublebondshi f
tsbot hn
π*and π π*t ransi
tionst ol ongerwav elengt hs.The ef fecton π π*band i smor e
pronounced.Woodwar dformul atedr ulest opredictt heposi ti
onofanabsor pti
onmaxi mum in
anunknownenone.Theser ul
eshav ebeensummar izedi ntable6.

Tabl
e6:
 3.Ar
omat
icCompounds

Thesi mpl estar omat i

ccompoundi sbenzene.I tshowst wopr i
mar ybandsat184( ε=
47,000)and202( ε=7400)nm andasecondar yf i
nest ructur
ebandat255nm ( ε=230i n
cyclohexane) .Subst i
tuentsont hebenzener ingal socausebat hochr omicandhy psochromi c
shift
s ofv ar
ious peaks.Unl ike dienes and unsat urated ketones,t he ef fects ofv ari
ous
substit
uent sont hebenz eneringar enotpr edictabl
e.Howev er,qualit
ativeunder st
andingofthe
eff
ect s ofsubst ituents on the char acteri
stics ofUV- Vis spectrum can be consi dered by
cl
assify i
ngt hesubst i
tuentsintoelectron-donatingandel ectron-withdrawinggr oups.(i)Eff
ectof
Substituentswi t
hUnshar edEl ectr
ons:Thenon- bondingel ectronsi ncreaset helengthofπ-
system t hroughr esonanceandshi f
tthepr i
mar yandsecondar yabsor pti
onbandst olonger
wav el
engt h.Mor ei st heav ai
labili
tyofthesenon- bondingel ectr
ons,gr eatertheshi ftwil
lbe.In
additi
on, thepr esenceofnon- bondi ngelectronsintroducest hepossi bil
it
yofn π*t ransit
ions.
Ifnon- bondingelect
ronisexci tedi nt otheextendedπ* chromophor e,theatom f rom whichi ti s
remov edbecomesel ectron- defi
ci entandt heπ-sy stem ofaromat icr i
ngbecomesel ectr
onr ich.
Thissi tuati
oncausesasepar ationofchar geint hemol eculeandsuchexci tedst at
ei scalleda
charge- tr
ansferoranelect ron-t
ransf erexcit
edst ate.I
ngoi ngfrom benzenet ot-butyl
phenol ,the
pri
mar yabsor pt
ionbandat203. 5nm shi f
tsto220nm andsecondar yabsorpt
ionbandat254
nm shi f
tsto275nm.Fur ther,thei ncreasedav ail
abil
ityofnel ectronsinnegat ivel
ychar gedt -
butylphenoxidei onshiftst hepr imar ybandf rom 203. 5to 236nm ( a32. 5nm shi f
t)and
secondar ybandshift
sf rom 254nm t o290nm ( a36nm shi f
t)(Figure12) .Bot hbandsshow
hyper chromiceffect
.Ont heot herhand, i
nthecaseofani li
nium cation,t
herearenonel ect rons
forinteracti
onandabsor ptionpr oper t
iesarequi tecloset obenzene.Buti naniline,theprimar y
bandi sshif
tedto232nm f rom 204nm i nanil
i
nium cat ionandt hesecondar ybandi sshiftedt o
285nm f rom 254nm (Figur e13) .

Fi
gur
e12:
UV-
spect
raoft
-but
ylphenol
andt
-but
yphenoxi
dei
nmet
hanol
 Fi
gur
e13:
UV-
spect
raofani
l
ineandani
l
ini
um sal
tinmet
hanol

(i
i
)Ef fectofπConj ugation:Conjugati
onoft hebenzener i
ngalsoshi
ftstheprimar
yband
at203.5nm mor eeffecti
vel
yt olongerwav el
engt handsecondar ybandat254nm i sshi
ft
edto
l
ongerwav elengtht olesserextent.Insomecases,t hepr i
mar ybandov er
takesthesecondar
y
band.Forexampl e,benzoicacidshowspr i
mar ybandat250nm andsecondar ybandat273nm,
butci
nnami cacidt hathaslongerchr omophoreexhi bitspri
mar ybandat273nm andsecondary
bandremainsmer gedwi t
hit.Similar
ly,
inbenzal dehyde,thesecondarybandappearsat282nm
andprimarybandat242nm buti ncaseofci nnamal dehyde,pri
marybandappear sat281nm
andremainsmer gedwi thsecondar yband( fi
gur e14) .Thehyperchromi
cef fectar
isi
ngdueto
ext
endedconj ugationisalsovisibl
e.

Fi
gur
e14:
UV-
spect
raofbenzal
dehy
deandci
nnamal
dehy
dei
nmet
hanol
 (
ii
i)Ef
fectofElectr
on-wi
thdr
awingandElect
ron-r
eleasingGroups:Elect
ron-
withdrawing
+
substit
uentsviz.NH3 ,SO2NH2,CN,COOH,COCH3,CHOandNO2 et c.havenoef fectont he
positi
onofsecondar yabsorpti
onbandofbenzener i
ng.Butt hei
rconjugati
onef fectswith
πelectr
onsoft hearomaticri
ngareobserv
ed.El
ectron-
donatinggroupssuchas- CH3,- Cl
,-Br,-
OH, -
OCH3, -
NH2et ci
ncreasebot
hλmaxandεmaxv
aluesofthesecondar yband.

Incaseofdi substi
tutedbenzeneder i
vati
ves,itisessent ialt
oconsi dertheeff
ectofbot h
thesubst i
tuents.I npar a-
subst i
tutedbenzenes,t wopossi bili
ti
esexist.Ifbot ht hegroupsar e
electron-donatingt hentheobser v edspectrum isclosertomonosubst i
tutedbenzene.Thegr oup
withst rongeref fectdetermi nestheext entofshifti
ngofpr imar yband.I fonegr oupiselectr
on-
releasingandot heri sel
ectron-withdrawing,t
hemagni t
udeofr edshiftisgr atercomparedt othe
effectofsi nglesubst i
tuenti ndi
viduall
y.Thisisat tr
ibutedt ot heincreasedel ect
rondri
f tfr
om
electron-donatinggr oupt ot heelectron-wi
thdrawinggr oupt hroughπ- bondofbenzener ing.For
exampl e,anil
ine shows secondar yband at285 nm whi ch due to pr esence ofel ectr
on-
withdrawi ngp-ni tr
osubst ituentisshi ft
edt o367nm wi t
hasi gnif
icanti ncreaseinabsor pti
vi
t
(fi
gure15) .

Fi
gur
e15:
UV-
spect
raofani
l
ineandp-
nit
roani
l
inei
nmet
hanol

Iftwogr
oupsofadi substi
tut
edbenzenederi
vat
iveareplacedort
ho-ormeta-toeach
other
,thecombinedeffectoft wosubsti
uentsisobserved.Incaseofsubsti
tut
edbenzoy l
deri
vati
ves,an empi
ri
calcor r
ection ofst
ructur
e wit
h observed posi
ti
on ofthe pri
mary
absorpt
ionbandhasbeendev eloped.Int
heabsenceofst eri
chindr
ancetoco-pl
anari
ty,t
he
cal
cul
atedv
aluesar
ewi
thi
n±5nm oft
heobser
vedv
alue.

(
iv)Pol
ycycl
icAromati
cCompounds:Incaseofpol ycy
clicaromat
ichydr
ocarbons,due
toextendedconjugat
ion,bot
hprimaryandsecondar
ybandsar eshiftedt
olongerwavelengt
h.
Thesespectraareusuall
ycompli
catedbutar
echaracter
ist
icofparentcompound.Thepr i
mary
bandat184nm i nbenzeneshif
tsto220nm incaseofnapht hal
eneand260nm i ncaseof
anthr
acene.

Si
milar
ly,t
hest
ruct
uredsecondar
ybandwhichappear
sasbroadbandaround255nm in
benzeneisshi
ftedto270nm and340nm respect
ivel
yincaseofnapht
haleneandanthr
acene
molecul
es.

Commer
cial
Appl
i
cat
ionsofUVandVi
sibl
eSpect
roscopy

TheUV- Vi sspectroscopyhasi nnumer abl

eapplicati
onsinthedr ugsandphar maceut i
cal
i
ndust ry
.Beer -Lamber tlaw of f
ersav aluableandsi mplemet hodf orquant itati
veanalysis.In
practi
ce,acal i
br ati
oncur veisconstructedbypl ott
ingabsorbancev s.mol arconcentrati
onand
theconcent rati
onofunknownwi th‘X’absorbancei sdeterminedbyf indingt heconcentration
correspondi ngt ot hemeasur edabsor banceont hecal i
brat
ioncurve.TheUVspect roscopyi s
usedext ensivelyi ndeterminingrateconst ants,equil
i
brium constants,acid-basedissociation
constant set cf orchemi calreacti
ons.TheuseofUVspect rometr
yi nev aluationofenzy mat i
c
assay s has become v erycommon e. g.the activi
tyofenzy me dehy drase is assayed by
measur ingt hef ormationofer goster
ol at282nm.

I
nfr
aredAbsor
pti
onSpect
roscopy(
Vibr
ati
onal
spect
roscopy
)
Thet woat omsj oi nedt oget herbyachemi cal bond( maybesi ngl e, doubl eort ripl
ebond) ,
macr oscopi call
ycanbecomposedast wobal l
sj oinedbyaspr ing.Theappl icationofaf or ce
l
ike( i
)st retchi
ngofoneorbot ht hebal l
s( atoms)awayf rom eachot herorcl osert oeachot her
(i
i)bendi ngofoneoft heat omsei therv erti
call
yorhor i
zont allyandt henr eleaseoft hef or ce
resultsint hev ibrati
onsont het wobal ls(atoms) .Thesev i
br ationsdependont hest rengt hof
thespr ingandal sot hemode( stretchingorbendi ng)i nwhi cht hef or cei sbei ngappl ied.
Simi l
arl
y, atordinarytemper atur es, organicmol ecul esarei naconst antst at eofv i
brations, each
bondhav ingi t
schar acter i
sti
cst retchingandbendi ngf r
equenci es.Wheni nfraredl ightradi ations
-
1
between4000- 400cm ( ther egi onmostconcer nedt oanor gani cchemi st )arepassedt hrough
asampl eofanor ganiccompound,someoft heser adiati
onsar eabsor bedbyt hesampl eand
areconv ertedintoener gyofmol ecul arv i
brat
ions.Theot herr adiationswhi chdonoti nt eract
wi t
ht hesampl ear etransmi t
t edt hr ought hesampl ewi thoutbei ngabsor bed.Thepl otof%
transmittanceagai nstf requencyi scal ledthei nf raredspect rum oft hesampl eorcompound.
Thisst udyofv i
brati
onsofbondsbet weendi f ferentat omsandv ar iedmul ti
pl i
cit
ieswhi ch
dependi ngont heel ctr
onegat ivity,massesoft heat om andt heirgeomet ryv ibrateatdi fferent
butspeci f i
edf r
equenci es;i scal ledi nfraredspect roscopy .Thepr esenceofsuchchar act erist i
c
vibrati
onalbandsi nani nf r
aredspect rum indicat est hepr esenceoft hesebondsi nt hesampl e
underi
nvest
igat
ion.

Hooke’sl aw andAbsor pti

onofr adiat i
onsThebandposi tionsintheI Rspect rum ar e
presentedinwav enumber s(ν)whoseuni tisther eci
procal centi
met er(
cm- 1).νisproportional
totheener gyofv i
brati
on.∆E=hυ=hc/λ=hcνTher efore,inpr i
nci
ple,eachabsor ptionof
radi
ationint hei nf
raredregionisquant izedandshoul dappearasshar pl i
ne.Howev er,each
vibr
ati
onalt ransiti
on withinthe mol eculei s associ ated wi th numberofr otati
onalener gy
changesandt husappear sascombi nationofv i
brat
ional-rotati
onalbands.Theanal ogyofa
chemicalbondwi thtwoat omsl i
nkedt hr oughaspr i
ngcanbeusedt orati
onalizesev eral
featur
esoft hei nfr
aredspect r
oscopy.Theappr oximationt ov ibr
ationfr
equencyofabondcan
bemadebyt heappl i
cat
ionofHooke’ slaw.I nHooke’ sl aw,t woat omsandt heirconnect i
ng
bondar etreatedasasi mplehar monicosci l
latorcomposedoft womassesj oinedbyaspr i
ng
andf r
equencyofv i
brati
onisstatedas

Theref
ore,thevibrat
ionalf
requencyofabondwoul di ncreasewiththedecr easein
reducedmassoft hesystem.Itimpl
iesthatC-HandO-Hstr
etchingabsorpti
onsshouldappear
athigherf
requenci
esthanC- CandC- Ostret
chi
ngfr
equenci
es.Similar
ly,O-
Hstret
chingshould
appearathigherf r
equencythanO- Dstretching.Fur t
her,i
npar al
lelwit
ht hegeneralknowledge
thatt
hest r
etchingofthespringrequir
esmor eener gythant obendit,t
hest ret
chi
ngabsor pti
on
ofabandal way sappearathi gherenergythant hebendingabsor pt
ionoft hesameband.The
Hooke’slaw canbeusedt ot heor
eti
callycalculatetheappr oximatestretchi
ngfrequencyofa
5
bond.Thev alueofKi sapproximately5x10 dy ne/cm forsingl
ebondsandappr oximatel
yt wo
andthreeti
mest hi
svaluef
ort hedoubleandt r
iplebonds,respecti
vel
y.

Letuscalcul
atetheapproxi
mat
efr
equencyoft
heC-
H st
archi
ngv
ibr
ati
onf
rom t
he
massesofcar
bonandhydrogen

mC=massofcar om =20x10-24g
bonat

mH =massofhy
drogenat 6x10-24g
om =1.

Letusconsi derhow t her adi ationsar ebei ngabsor bed.Weknow t hatator dinary
temper ature,moleculesar einconst antst at eofvibrations.Thechangei ndipolemomentdur i
ng
vibrationoft hemol eculeproducesast ationaryalternatingel ectri
cf i
eld.Whent hefrequencyof
i
nci dentel ectromagnet i
cr adi at i
ons i s equalt ot he al t
ernat i
ng electr
icf ield produced by
changesi nthedi polemoment ,t her adiationi sabsor bedandv ibr
ationallevelsoft hemol ecule
areexci t
ed.Oncei nthev ibrati
onal lyexci t edst at
e, t
hemol ecul escanl ooset heex traener gyby
rotat i
onal,col l
isi
onort ranslationalpr ocesseset c.andcomebackt ogr oundst at
e.Ther ef ore,
onlyt hosev i
brationswhi chr esul tinar hyt hmicalchangei nt hedipolemomentoft hemol ecule
absor bi nfraredr adiati
onsandar edef i
nedasI R act i
v e.Theot herswhi chdonotunder go
changei ndi polemomentoft hemol eculear eIRi nactivee.g.t hest r
etchi
ngofasy mmet ricall
y
subst itut
edbond,v iz‘carbont ripl
ebondcar bon’i nacet yleneandsy mmet ricalstretchingi n
carbondi oxide( f
igure17)–al inearmol ecul e,producenochangei nt hedipolemomentoft he
syst em andt hesev i
brati
onscannoti nteractwi thinfraredl i
ghtandar eIRinactive.Ingener al,the
funct i
onal groupst hathav east rongdi polegi veri
set ost rongabsor pti
onbandsi ntheI R.

Modesofmol
ecul
arv
ibr
ati
ons

Molecul es withl arge numberofat oms possess a l ar

ge numberofv i
brat
ional
fr
equencies.Foranon- li
nearmol eculewi t
hnat oms,thenumberoff undamentalvi
brat
ional
modesis( 3n-6);l
inearmol ecul
eshav e3n-5fundamentalv i
brat
ionalmodes.Therefore,wat
er-a
non-l
i
nearmol eculetheoreti
cal
lypossesses3f udamentalvibr
at i
ons–t wost r
etchi
ngandone
bendi
ng ( f
igure 16);wher eas carbon dioxi
de -a l i
nearmol ecul
e possess 4 fundamental
absorpt
ionbandsi nvol
vingt wostret
chingandt wobendi ngmodes( fi
gure17).Amongstthese
theor
eti
call
ypossi blevi
brat
ions,astr
etchi
ngvi
brati
onisarhy t
hmicalmovementalongthebond
axissuchthatinteratomicdist
anceisincr
easi
ngordecreasing.Abendi
ngv i
brati
onconsist
sof
achangei nbondangl ebetweenbondswi thacommonat om orthemov ementofagr oupof
atomswi t
hr espectt oremaini
ngpartoft hemolecul
ewithoutmov ementoft heatomsinthe
groupwithrespectt ooneanother.

Fi
gur
e16:
Vibr
ati
onal
modesf
orwat
ermol
ecul
e

Fi
gur
e17:
Vibr
ati
onal
modesf
orcar
bondi
oxi
demol
ecul
e

Thev ari
ousstr
etchingandbendingmodescanber epresentedbyconsi deri
nganAX2
group appeari
ng asapor ti
on ofmolecule,forexample,t heCH2 gr oup i
n ahy drocarbon
molecule(fi
gure18).Anyat om joi
nedtotwoot heratomswi llundergocompar ablevibrati
ons
forexampl eNH2 orNO2.Each ofdi ff
erentv i
brat
ion modesmaygi veriseto a differ
ent
absorpti
onbandsot hatCH2gr oupsgiver i
set otwoC- H st r
etchingbandsi .e.υsym and
υanti
sym.Someoft hevibrati
onsmayhav et hesamef requencyi .e.theyaredegenerateand
thei
rabsorpti
onbandswillappearatsameposi t
ion(f
orCO2,seef igure17).
 Fi
gur
e18:Vibr
ati
onal
modesofaCH2gr
oup.[andi
ndi
cat
emov
ementabov
eandbel
ow
t
hepl
aneofpage]

In additi
on tot he fundamentalv i
brati
ons,ot herf r
equenci es can be gener ated by
modul ati
ons oft he fundamentalbands.Ov ertone bands appearati ntegralmulti
pl es of
onsatsay800cm and1750cm-1 wi
-
1
fundament alv i
brati
ons.Therefore,thestr
ongabsor pt
i ll
-
1 -
1
alsogi v
er i
set oweakerabsor pti
onsat1600cm and3500cm , respectively.IntheI
Rspect ra
ofbenzal dehyde( fi
gure33)andacet ophenone( fi
gure31) ,duet oC=Ost retchi
ngvibrat i
ona
weakov eronecanbeseenat3400and3365cm-1,r
t especti
vely.Twof requenci esmayi nt er
act
-
1
togiv ebeatswhi charecombi nationordif
ferencef r
equencies.Theabsor ptionsatxcm andy
-
1
esatx+ycm andx–ycm-1.Ther
-1
cm i nt
eracttopr oducet woweakerbeatf requenci efore,
wher easthef actorsl
ikedegeneracyofbandsf r
om sev eralabsorpti
onsoft hesamef requency ,
l
ackofchangei nmol eculardi
polemomentdur ingv i
brat
ionandf alloffrequenci esoutsidet he
4000-400cm-1 regiondecreasethenumberofbandswher eastheov ert
oneandbeat sincrease
thenumberofbandsact uall
yappear edinI R spectr
um.Ther efore,theoreti
calnumber sof
fundament al f
requencies are sel dom obser v
ed. Ot her Factors Infl
uencing Vibrati
onal
FrequenciesThev ibr
ati
onalfrequencyofabond,bei ngpartofamol ecule,issignif
icantl
y
affectedbyt heel ectr
oni
candst er i
cf act
orsoft hesur r
oundings,inaddi ti
ont othebond
strengthandat omi cmassesdi scussedabov e.Whent wobondosci ll
atorsshar eacommon
atom,t heysel
dom behav easi ndi
vidualoscill
atorswher etheindivi
dualoscil
lati
onfrequencies
are wi del
y di
fferent.The mechani calcoupling int
eracti
ons between t wo oscill
ators are
responsibl
eforthesechanges.

Forexampl e,t hecar bondi oxidemol ecule,whi chconsi stsoft woC=O bondswi tha
commoncar bonat om,hast wof undament alstretchingv ibrati
ons– anasy mmet ri
calanda
symmet ricalst retchingmode.Thesy mmet r
icalstretchingmodepr oducesnochangei ndi pol
e
momentandi sIRi nactive.Asy mmet ricst
retchingmodei sIRact iveandappear satahi gher
-1 -
1
fr
equency( 2350cm )t hanobser vedf oracarbony lgroupi nal i
phaticketones( 1715cm ) .The
-
1
carbonyl stretchingf requencyi nRCOCH3( ~1720cm )i slowert hanaci dchlori
deRCOCl (1750-
-1
1820cm ) .Thischangei nfrequencyoft heC=Ost r
etchingmaybear isi
ngduet o(i)di
fference
i
nmassbet weenCH3andCl( i
i)t
hei nducti
veormesomer i
cinfluenceofClont heC=Obond( ii
i
)
coupli
ngi nteractionsbet weenC=OandC- Clbonds( iv)changei nbondangl esar isi
ngduet o
steri
cfact or set c.Iti susuallyimpossi bl
et oisolateoneef f
ectf r
om t heot her.Howev er,the
appropriateemphasi scanbepl acedont hosef eatur esthatseem t obemostr esponsiblein
explai
ningt hechar act er
isti
cappear anceandposi tionofgr oupf requencies.

Sampl
ePr
epar
ati
on

Forr ecor dinganI Rspect rum,t hesampl emaybegas,al iqui d,asol idorasol uti
onof
anyoft hese.Thesampl esshoul dbeper fectl
yf reeofmoi sture,sincecel lmat erials(NaCl,KBr ,
CsBret c.)ar eusual l
yspoi l
edbyt hemoi sture.Liqui dsar estudi edneatori nsol ution.Incaseof
neatl i
qui d,at hinf il
m of<0. 01mm t hi
cknessi sobt ainedbypr essi ngt heliquidbet weent wo
sodium chl ori
depl atesandpl atesar esubj ectedt oI Rbeam.Spect r aofsol ut i
onsar eobtained
byt aki
ng1- 10%sol utionoft hesampl einanappr opr i
at esolv entincel lsof0. 1-1mm t hi
ckness.
Acompensat i
ngcel l
, containingpur esolv entispl acedi nther eferencebeam oft hei nstrument.
Thechoi ceofsol ventdependsont hesol ubil
it
yoft hesampl eandi t
sownmi nimal absorpti
oni n
IRr egion.Car bont etrachlori
de,chl oroform andcar bondi sul f
idear epr eferredsol vents.The
spect r
um ofasol idcanbeobt ainedei therasamul lorasanal kal ihal i
depel l
et.Mul l
sar e
obtainedbyt horoughl ygrinding2- 5mgofasol idsampl ewi thadr opofmul l
ingagentusual l
y
Nujol( mi xtureofpar afini
chy drocar bons)orf luor olube( acompl et elyf luorinatepol ymer )
.The
suspendedpar t
iclesmustbel esst han2µM t oav oi dexcessi vescat teringofr adi ati
ons.The
mul lispl acedbet weent wosodi um chl or i
depl atesandpl atesar esubj ectedt oI Rbeam.For
preparing, anal kalihal idepellet,1-2mgofdr ysampl ei sgr i
ndedwi t h~100mgofKBrpowder .
Themi xtur eist henpr essedi ntoat ranspar entpel letwi thaspeci aldi eunderapr essureof
10,000-15, 000psi .KBrpel letist henmount edonhol derandi spl acedi nsampl ebeam ofI R
spect r
ophot omet er.
Char
act
eri
sti
cGr
oupVi
brat
ionsofOr
gani
cMol
ecul
es

Ani nfrar
edspect r
um ofanor ganiccompoundcompr isesmanybandsandassi gning
eachbandt oapar t
icul
armodeofv ibr
at i
oni spr act
icall
yi mpossi bl
ebutt wonon- ident i
cal
mol eculesgener all
yhav edi f
fer entIRspect ra.AnI Rspect r
um,t herefore,isaf ingerpri
ntoft he
mol ecule.Ther egionmostusef ulforthepur poseof“ fingerpr
inti
ng”oft hecompoundi s650-
-1
1350cm .Thi sregioncompr isesal ar
genumberofbandsduet oskel etalv i
brati
onsandwhen
thespect rum wear est udyingcoi nci
desexact lywi t
ht hespect r
um ofaknowncompound, itcan
-1
besaf elyassumedt hatthet wocompoundsar eidentical.Ther egionabov e1350cm of t
en
provideseasi lyr ecognizable bandsofv ariousf unctionalgr oupsand t husmuch v aluable
structuralev i
dencef rom relati
v elyfew oft hesesbandsi sobtainedandt otalinter
pretationof
thecompl etespect rum issel dom r equi
red.I nthef oll
owi ngsections,t hebasi cinformat i
on
aboutt hev i
brati
onal modesi nbasi cfuncti
onal groupshasbeendi scussed.

1.Hy
drocar
bonsC-
HandC-
Cst
ret
chi
ngandbendi
ngv
ibr
ati
ons

(
i)Alkanes:Insi
mplehydrocar
bons,onlytwot y
pesofat oms-CandH andonl ytwo
ty
pesofbonds–C- CandC-H arepresent.TheC-H st
archingvi
brat
ionsusual
l
yoccuri
nthe
-1 -
1
gener
alregi
onbet ween3300cm ( i
nalkynes)and2700cm ( inal
dehydes)
.

Ahy dr
ocar
boncont ai
ningamet hylgr
oupusuallyshowstwodist
inctbands,oneat2960
-
1 -1
cm duet oasymmetri
cstretchingandt heotherat2870cm duet osymmet r
icstret
chi
ng.The
C-Hbondsinmethyl
enegr oupunder gonumberofst retchi
ngandbendi
ngv i
brati
onsasshown
i
nfigur
e18.Thetwost r
etchingv ibr
ati
ons–asy mmet ri
calandsymmetr
icaloccurat2925cm-1
andappeari
nthespectr
um wi thinarangeof±10cm-1.

TheC- Hbendi ngv i

brationsoft hemet hylgr oupsi nt hehy drocarbonsnor mall
yoccurat
-
1 -
1
1450and1375cm .Thebandat1375cm i sduet omet hy lont hecar bonat om andi squi
te
sensit
ivetot heel ectronegat i
vityofthesubst it
uentpr esentatt hemet hylgr oup.I tshi
ftsfr
om as
-1 -
1
highas1475cm i nCH3- Ft oasl owas1150cm i nCH3- Br.Howev er
,t hisbandi sextr
emely
usefulindet ectingt hepr esenceofmet hylgroupi nacompoundbecausei tisshar pandof
medium i ntensityand i sr arelyov erl
apped byabsor pt
ions due t o met hylene ormet hi
ne
deformations.Thei nt ensit
yoft hi
sbandusual lyincr easeswi t
ht henumberofmet hylgr
oupsin
thecompound.Howev er,thepr esenceoft woormor emet hylgroupsononeal i
phati
ccarbon
atom (i
sopr opy lort -butylgroups)r esult
si nsplittingoft hisbandduet oin-phaseorout -
of
phaseinteractionsoft hetwosy mmet r
icalmet hy
l def ormations.

Incaseofmet hyl
enegroup,C-Hbendingv i
brati
onssuchasscissor
ing,t
wist
ing,waggi
ng
andr ockingnor mallyappearatf airl
ydif
ferentfrequenci
es.Iftwoormor eCH2gr oupsare
present,theusuall
yst rongsci
ssori
ngandr ockingabsorpti
onbandsappearat1465and720cm
-
1
,respectivel
y.Wher easweakbandsduet ot wist
ingandwaggi ngvibr
ati
onsappearat1250+
-
1
100cm .So, thescissoringabsor
ptionbandofmet hy
lenearound1465cm-1oft
enov er
lapswi
th
asy
mmet
ri
cbendi
ngv
ibr
ati
onofmet
hyat1450cm-1.
l

Incy cli
cal i
phati
chydrocar
bons,theC-Hst retchi
ngfrequenciesarethesame(2800–
-
1
3000cm )asi nthecaseofacy cl
iccompounds,ift heringi
sunst r
ained.However
,methyl
ene
-
1
nhexaneand1448cm 1 i
-
scissori
ngbandsshi f
tsli
ghtl
ytosmal l
erwavenumber( 1470cm i n
cyclohexane, seefigure19)
.Inster
ical
l
ystrai
nedcy cli
ccompounds, theC-Hstret
chi
ngnormall
y
-
1
occursatslight l
yhigherwavenumbere.g.3080-3040cm i ncycl
opropane.

TheC-Cbondv i
brat
ionsappearasweakbandsi 800cm-1r
n1200- egi
onandar
esel
dom
-
1
usedforstr
uctur
alstudy.WhereastheC-Cbendi
ngabsor
pti
onsoccurat<500cm andare
usual
l
ybelowtherangeofIR–i nst
rument.

Fi
gur
e19:
Thei
nfr
aredspect
rum ofcy
clohexane(
neatl
i
qui
d)

(i
i
)Alkenes:Thecar bon-carbondoublebondhasahi gherfor
ceconstantthanaC- C
singl
ebondandi nanon-conjugatedolef
in,C=Cst
retchi
ngv
ibr
ati
onsappearathi
gherfrequency
-
1 -1
(1680-
1620cm )t hanthatoft heC-Cstarchi
ngvi
brati
ons(
1200-800cm ) .

In compl etel
ysy mmet ri
calalkenes,such aset hy l
ene,t etr
achloroet hyl
eneet c.,C=C
str
et chingbandi sabsent ,duetolackofchangei ndipol emomenti ncompl etel
ysy mmet rical
molecul e.On t he ot herhand,non- symmetricallysubst ituted doubl e bonds exhi bi
tst r
ong
absor ptionbands.Theabsor pt
ionbandsar emor eintensef orci sisomer sthanf ort rans
i
somer s; formonoort risubstit
utedolefi
nsthanf ordiandt et rasubst i
tutedones.Al so,t
ermi nal
ol
efinsshow st r ongerC=C doubl ebond st retching vi
br ationst han i
nt ernaldoubl ebonds.
Similarl
yC=Cgr oupsconj ugatedwi t
hcer t
ainunsat ur
atedgr oupshow st rongerbandt hanf or
non-conj ugatedones.I ncaseofol efi
ns,conjugat edwi t
hanar omat i
cring,t heC=Cst r
etching
appear sat1625cm-1 ( s)andanaddi t
ionalbandat~1600cm-1 i sobser vedduet oaromat ic
doubl ebond.I ncompoundscont ai
ningbotholefinicandal ky lC-Hbonds, t
hebandsabov e3000
-
1
cm ar egener allyattri
but edtoaromat i
coral i
phat i
cC- H st retching,wher easbet ween3000-
-
1
2840cm ar egener all
yassi gnedt othealkylC- H stretching.Theabsor pt i
onf requencyofa
doubl ebondi nacy cli
cr i
ngi sverysensiti
vetor ingsize( figur e20) .Theabsor pti
onf r
equency
decr
easesast heint
ernalangledecreasesand i
slowesti
ncy
clobut 90o angl
ene( e).The
fr
equencyi
ncr
easesagainforcy
clopr
opane.

Fi
gur
e20:
C=Cv
ibr
ati
onf
requenci
esofcy
cloal
kenes

Theexocy cli
cdoublebondsexhibi
tani ncr
easeinfrequencywit
hdecreaseinr
ingsize(
figur
e
-
1
21).Theex ocycl
i
cdoubl ebondonsix-memberedri
ngabsor bsat1651cm andi ti
sshif
tedto
-1
1780cm i ncaseofexocy cl
i
cdoublebondoncy clopr
opane.Theall
enesshow thehi
ghest
-1
doublebondabsor pt
ionsat1940cm .

Fi
gur
e21:
Exocy
cli
cC=Cdoubl
ebondf
requenci
esi
nvar
iousr
ingsi
zes

(i
ii)Alky nes:Al lalkynesbot ht erminal( R.C≡CH)ornon- t
ermi nal( R.
C≡CR)cont ai
ncar bon–
carbont ri
plebondbutt henon- t
er minalalky nesal socont aina≡CHbond.Thef orceconst antfor
at ri
plebondi sgr at
ert hant hatf oradoubl ebond.Consequent l
y ,wher easaC- Cst retching
vibrati
onsoccurbet ween1300- 800cm- 1andt heC=Cst retchingv ibrati
onoccuri nther egion
-
1
1700- 1500cm , t
heC≡Cv ibrati
onsar eobser vedatsi gnif
icantlyhigherf requenciesinther egion
of2300t o2050cm- 1.Thet ermi nalalkynesshowweakt ri
plebondst r
etchi ngvi
brati
onat2140-
2050cm-1, wher eastheunsy mmet r
icall
ydi subst i
tutedalkynesshowat ri
plebondabsor pt i
onat
-1
2260- 2190cm .Theacet yl
eneC- H st retchingv ibrat
ionsar enor mal l
yobser vedasashar p
char acteri
sticbandi nt heregion3310- 3200cm- 1andt heacet yl
enicC- H bendi
ngv i
brations
-1
occuri nt her egi on600- 650cm .Ther ef oret hef requencyoft heabsor ptionofC- Hbondi sa
funct i
onoft het y peofhy bri
dizat i
onoft hecar bont owhichhy drogenat om isattached.Whi l
e
3 2
mov i
ngf rom sp t osp andsphy br
idizedcar bons, thes-charact erincreasesandsoi sthebond
strength( forceconst antofC- Hbondandt hef requencyofabsor ption( Table7).

Tabl
e7:
(i
v)Ar omat i
cHy dr
ocarbons:I nthear omat i
ccompounds,t hemostpr omi nentbandsar edueto
-1
out -
of-pl
anebendingofr i
ngC- Hbondsi ntheregi onof900-650cm .Thesebandscanbeused
toassi gnt heri
ngsubst itutionpat t
erninmonosubst it
utedbenzenesand1, 2-,1,3-,and1, 4-
subst i
tuted benzene der ivatives. Mono subst it
uted benzene der i
vati
ves exhi bi
t st r
ong
absor pti
onbandnear690cm- 1( seeI Rspect rum oftoluene,fi
gure22) .Theabsenceoft his
bandi ndicatestheabsenceofmonosubst it
utedpheny lri
ngsint hesampl e.Asecondst r
ong
-1
bandappear sat~750cm .1, 2-Disubsti
tutedbenzenesgi veonest rongabsor pti
onbandat~
750cm-1.1, 3-Di
substi
tutedr i
ngsgi vet hr
eeabsor pt
ionbandsat~690, ~780and~880cm-1.1, 4
-
1
-Disubstitut
ed r
ings gi
ve one st r
ong absor ption band int he r
egi on 800-850 cm ( str
ong
-
1
absor pti
onbandat831cm i sseeni nIRspectr um oft-
butyl
phenol,figure26) .Thespect raof
aromat iccompoundst ypical l
yexhi bitmanyweakormedi um int
ensityC- Hst r
etchi
ngv ibr
ati
ons
-
1
i
nt her egion3100-3030cm , theregi onofolefi
ni ccompounds.
Fi
gur
e22:
Thei
nfr
aredspect
rum oft
oluene(
neatl
i
qui
d)

Fi
gur
e23:
Thei
nfr
aredspect
rum ofmesi
tyl
ene(
neatl
i
qui
d)

Thebandsconsi deredtobeofmosthel pindi

agnosingthearomaticchar
acterofthecompound
appearintheregion1650-1400cm-1.Ther
earenormallyfourbandsinthi
sregionatabout1600,
1585,1500and1450cm-1andar eduetoC=Cin-pl
anev i
brati
ons(seespectr
ainfigur
es22and
-1
23).Thecombi nati
onandov er
tonebandsin2000-1650cm r egi
onarealsocharacter
ist
icsof
aromaticr
ings.Mor eov
er,theyareveryweakandareobser v
edonlyinthecaseofconcent rat
ed
solut
ionsofhighlysymmet ri
cbenzenederi
vat
ives.

2.Al
cohol
sandPhenol
s

Whenahy drogenat
om from anal
iphat
ichydrocar
bonisreplacedbyanOHgr oup,new
bandscorr
espondingtonewOHandC- Obandabsor pti
onappearintheIRspect
rum.Amedi um
-1
to st
rong absor
pti
on band f
rom 3700 t
o 3400 cm (seeI R spectr
aof1-butanoland t-
butyl
phenoli nfigures25 and26)i sast rongindi cationt hatthesampl eisanal coholorphenol
(Thepr esenceofNHormoi sturecausessi milarr esul t
s).Theexactposi ti
onandshapeoft his
banddependsl argelyont hedegr eeofH- bonding.Ast rong,shar ppeakinther egionashigher
-1
3700cm i ngaseousorext remelydilutesolutionsr epresentsunboundedorf r
eeOHgr oup(s).
Alcoholsandphenol si ncondensedphases( bulkl i
qui d,KBrdi scs,concent
ratedsoluti
onet c.)
arestrongl yhy drogenbonded,usual lyint hefor m ofdy nami cpolymericassociati
on;di
mmer s,
tri
mers,t etramer set c.(Figure24)andcausebr oadenedbandsatl owerf requenci
es.The
hydrogenbondi nginvolvesal engtheningoft heor iginalO-Hbond.Thi sbondi sconsequent l
y
weakened, forceconst anti
sr educedandsot hest r
et chingfrequencyislowered.

Fi
gur
e24:
Pol
ymer
icassoci
ati
onofROH

TheC-Ost r
etchi
nginphenols/al
coholsoccur
satal owerfrequencyrange1250-1000
-
1
cm .ThecouplingofC- Oabsor
ptionwi
thadjacentC-
Cstret
chingmode,makesi tpossi
bleto
-1 -
1 -1
di
ff
erenti
atesbetweenprimar
y(~1050cm ) ,
secondar
y(~1100cm )andt er
ti
ary(~1150cm )
-
1
al
coholsandphenols(~1220cm ) .

Fi
gur
e25:
Thei
nfr
aredspect
rum of1-
but
anol
(neatl
i
qui
d)
 Fi
gur
e26:
Thei
nfr
aredspect
rum oft
-but
ylphenol
(nuj
olmul
l
)

3.Car bony lCompoundsTheabsor ptionpeakf orC=Ost retchi

ngi nt heregion1870t o
-
1
1600cm i sper hapst heeasi estbandt or ecognizeinI Rspectrum andi sextremel yusefulin
analysisofcar bonylcompounds.Thechangesi nC=Ost retchi
ngf r
equencyi nv ariouscarbonyl
compoundsv iz.aldehy des,ketones,acids,est er
s,ami des,acidhalides,anhy dr
ideset c.canbe
explained byconsi der i
ng ( i
)electronic and mass ef fects ofnei ghboring subst i
tuents(ii
)
resonanceef fects(bot hC=C andhet er
oat om l onepai r)(i
ii
)hy drogenbondi ng( int
erand
i
ntramol ecular)( i
v)ringst rainetc.Itiscust omar ytor efertotheabsor pti
onf requencyofa
-1
saturatedal i
phat i
cket oneat1715cm asnor malv al
ueandchangesi ntheenv i
ronmentoft he
carbony lgroupcanei therl owerorraiset heabsor ptionfr
equencyf rom the“ normal”v al
ue.

(i)I
nduct i
veandResonanceEf fects:Ther epl
acementofanal ky
lgroupofthesat ur
ated
aliphaticketonebyahet eroatom (
O,N)shi ftstheC=Ost r
etchingf r
equenciesduetoi nducti
ve
andr esonanceef f
ects.Inest er
s,theoxy genduet oinductiveeffectwi t
hdrawstheel ect
rons
from car bonylgroup( fi
gure27)andi ncreasest heC=Obondst rengthandt husthefr
equencyof
absor pti
on.I nami des,duet otheconjugationofl onepairofel ectronsonni t
rogenat om,the
resonanceef fectincreasest heC=Obondl engthandr educest heC=Oabsor pti
onf r
equency.
Ther efore,C=Oabsor ptionf r
equenciesduet oresonanceef fectsinami desareloweredbutdue
toi nductiveeffectinestersareincr
easedt hant hoseobservedinket ones.

Fi
gur
e27:
Induct
iveandr
esonanceef
fect
sinest
erandami
degr
oups
 Inaci
dchlor
ides,t
hehalogenat om st r
engthenstheC=Obondt hroughinducti
veef
fect
andshif
tstheC=O stret
chingfr
equenci esev enhi gherthanarefoundi nesters.Theacid
anhy
dri
desgiv
etwobandsi nC=Ost retchingfrequencyregionduet
osy mmetri
c( ~1820cm-1)
andasy
mmet r
ic(
~1760cm- 1)st
retchingv i
brati
ons(figur
e28).

Fi
gur
e28:
Induct
iveef
fecti
naci
dchl
ori
deandC=Ost
ret
chi
nanhy
dri
de

(i
i)Conjugat i
on Effect
s:The C=O st ret
ching fr
equencies forcar bon-car
bon double bond
-
1
conjugated systems ar e generall
yl ower by 25-45 cm t han those of correspondi ng
nonconjugatedcompounds.Thedel ocali
zati
onofπ-elect
ronsi ntheC=OandC=Cbondsl eadt o
part
ialdoublebondchar acterinC=OandC=Cbondsandl ower stheforceconstant(fi
gure30) .
Greaterist heabil
ityofdel ocal
izat
ionofel ect
rons,themor ei sloweringinC=O st retching
fr
equency .I n general s-cis conformati
ons absor b at hi gher frequency than s- trans
conformations.A simil
arlower i
ngi nC=O st r
etchi
ngf r
equencyoccur swhenanar ylringi s
conjugatedwithcarbonylcompound.

Fi
gur
e30:
Resonanceef
fect
sands-
cisands-
tr
ansst
ruct
uresi
nenones

(i
ii
)RingSi zeEf f
ects:Si
x-member edri
ngswithcar bonylgr oupe.g.cycl
ohexanoneabsor bat
-1
normalv aluei.
e.1715cm .Decr easeinri
ngsi zei ncr
easest heC=O st retchi
ngfrequency.
Smal l
erri
ngsr equiretheuseofmor ep-char
actertomakeC- Cbondsf ort herequi
sit
esmal l
angles.Thisgi
v esmor escharactertot
heC=Osi gmabondandt husresult
si nstr
engt
heningof
C=O doubl ebond.Thecompar isonofC=O stretchingf r
equenciesofv ari
ouscompoundsi n
fi
gure31showst hati
nketonesandest s,~30cm-1 i
er ncreaseinfrequencyoccursonmov i
ng
toonecar bonl
owerr i
ng.
Fi
gur
e31:
C=Ost
ret
chi
ngf
requenci
esi
nvar
iouscompounds

(i
v)HydrogenBondingEff
ects:Hydrogenbondingt oaC=O gr oupwi t
hdr awselect
ronsfr
om
oxygenandlowerstheC=Odoublebondcharact er
.Thisresult
sinloweringofC=Oabsor pt
ion
fr
equency.Moreeff
ecti
vei
sthehydrogenbonding,higherwi
llbetheloweringinC=Oabsorpt
ion
fr
equenci
es.

Fi
gur
e32:
H-bondi
ngef
fect
sonC=Ost
ret
ch

The monomer i
c carboxyli
c acids (i
nv ery dil
ute solut
ions)absorb at~1760 cm-1.The
dimerizat
ionofcarboxy l
i
caci dsi ntheirconcentratedsoluti
onsori nsoli
dst atelowersthe
-1
carboxylcar
bonylfr
equencyt o1710cm .Themor eeffecti
veint
ramolecul
arhydrogenbonding
-1
i
nmet hyl
sali
cyl
atelowerst heC=Ostretchingfrequencyto1680cm t hanobser
v edat1700cm
-
1
i
ncaseofmet hylp-hydroxybenzoat
e.

a.Al
dehy
desandKet
ones

Aliphati
caldehy desshowst r
ongC=Ost r
etchingintheregionof1740–1725cm-1.The
conjugationofanal dehydet oaC=Corapheny lgrouplowersC=Ost retchingby~30cm-1.
Thisef f
ectisseeni nbenzaldehydeinwhichar ylgroupisattacheddirectlyt
ot hecarbonyl
-
1
groupandshi ftsC=Ost retchto1701cm ( seeIRspectrum ofbenzal dehyde,fi
gure33) .
AldehydeC- Hst r
etchingv i
brat
ionsappearasapai rofweakbandsbet ween2860- 2800and
2760-2700cm-1.Thehi gherC- H st
ret
chingband( 2860-2800cm-1)ofal dehydei soft
en
-1
buri
edunderal iphaticCHband.Butt helowerC- Hbandat2760- 2700cm i susual
lyusedto
di
stinguishaldehydesf rom ketones.TheC- Hbendi ngv i
brati
onsappearbet ween945-780
 cm-1.

Fi
gur
e33:
Thei
nfr
aredspect
rum ofbenzal
dehy
de(
neatl
i
qui
d)

Theal i
phaticacycli
cket
onesshowC=Ost retchi
ngbetween1720to1700cm- 1whi chi
sshif
ted
tolowerf r
equenciesby20-
30cm- 1onconjugati
onwithC=Corphenyl
r i
ng.Thepresenceoftwo
conjugatedgroupsasinbenzophenonefur
therlower
st heC=Ost
ret
chingfrequencyto1665cm-
1
(f
igures34and35) .
Fi
gur
e34:
Thei
nfr
aredspect
rum ofacet
ophenone(
neatl
i
qui
d)

Fi
gur
e35:
Thei
nfr
aredspect
rum ofbenzophenone(
nuj
olmul
l
)

I
ncaseofcy
cli
cketones,t
hecoupl i
ngbetweenC=Ostr
etchi
ngandC(=O)-
Csi
ngl
ebondcauses
i
ncr
easei
nC=Ostretchi
ngfrequencyastheC-C(
=O)angl
edecreases(
fi
gur
e31)
.

b.Car boxy l
i
cAci ds,EstersandCar boxy l
atesIncaseofcar boxy l
i
caci ds,i
nsolidst ateorpure
l
iquidst ate,theintermolecul
arhy dr ogenbondi ngweakenst heC=Obondandt husl owerthe
-1
str
etchingf requencyt o~1720cm .TheO- H st
retchappearsasav erybroadbandbet ween
-
1
3400–2500cm ( seeI Rspectrum ofbenzoi cacid,fi
gur
e36) .Theappear anceofst r
ongC=O
-
1
str
etchingal ongwi thbroadhy droxy lpeakcent er
edat~3000cm i nanI Rspect rum cert
ainl
y
showst hepr esenceofcar boxy l
icaci d.Inaddi t
ionamedi um intensit
yC=O str etchappears
between1320–1260cm-1.I ndi l
utesol uti
ons,thecarboxyl
i
caci dsattainmonomer icstr
uctur
es
andt hei nductiv
eef fectofoxy genshi ft
st heC=O absorpti
onbandt ohigherval ues(1760–
-1
1730cm )t hanobservedinket ones.
Fi
gur
e36:
Thei
nfr
aredspect
rum ofbenzoi
caci
d(nuj
olmul
l
)

Incaseofest er
s,theC=O str
etchi
ngappearsintherange1750-1730cm-1 andstrongC-
O
-
1
str
etchi
ngabsorpti
onappear
sint herange1300-1000cm .Theest er
sofα,β-unsat
urat
edor
aryl
carboxy
li
cacidsduetoconj
ugati
onabsorbatl
owerfrequency(
fi
gure37)
.

Fi
gur
e37:
Eff
ectofconj
ugat
ioni
ncy
cli
cest
ers

ROTATI
ONALSPECTROSCOPY(
MICROWAVESPECTROSCOPY)

I
ntr
oduct
ion

Freeat omsdonotr otat eorv ibrate.Foranosci l

latoryorar ot ationalmot ionofa
pendul um, oneendhast obet i
edorf i
xedt osomepoi nt.I
nmol eculessuchaf ixedpoi ntisthe
centerofmass.Theat omsi namol eculear ehel dt ogetherbychemi calbonds.Ther otational
andv ibr ati
onalener gi
esar eusual l
ymuchsmal lert hant heener gi esr equiredt obr eakchemi cal
bonds.The r otati
onalener gies cor respond t ot he mi cr
owav er egion ofel ect romagnet i
c
10 12
radiation( 3x10 t o3x10 Hz;ener gyr angear ound10t o100J/ mol )andt hev i
brational
12 14
energiesar eint hei nf
rar edr egion( 3x10 t o3x10 Hz;ener gyr angear ound10kJ/ mol )ofthe
electromagnet icr adiation.Forr igidr otors( no v i
brati
on dur ing r otation)and har moni c
oscill
at ors(wher ei
nt her ear eequaldi splacement sofat omsonei thersi deoft hecent erof
mass)t here ar e simpl ef or mul ae char acteri
zing t he mol ecul arener gyl ev els.I nr eall i
f e,
mol ecul esrotateandv ibratesi mul taneousl yandhi ghspeedr otat i
onsaf f
ectv ibrat ionsandv ice
versa.Howev er ,i
nouri ntroduct oryv iewofspect r oscopywewi llsimpl ifythepi ctur easmuchas
possibl e.Wewi llfi
rsttakeupr ot ati
onal spect r
oscopyofdi atomicmol ecules.

Rot
ati
onal
Spect
raofdi
atomi
cs
Figur
e38:
Arigi
ddi
atomi
cwi
thmassesm1andm2j
oinedbyat
hinr
odofl
engt
hr=r
1+r
2.The
centr
eofmassi
satC.

Thetwoi ndependentrot
ationsofthi
smol ecule( Fi
gure38)arewithrespecttothet
wo
axeswhi chpasst houghC andar eperpendi
culartot he“ bondlength”r.Ther ot
ati
onwith
respecttothebondaxi sispossibl
eonlyfor“cl
assical”objectswi
thlargemasses.Forquant
um
objects,a“r
otati
on”withrespecttothemolecul
araxisdoesnotcor respondtoanychangeinthe
mol ecul
east henewconf i
gurati
oni si
ndi
sti
ngui
shabl efrom theol
done.

Thecent
erofmassi
sdef
inedbyequat
ingt
hemoment
sonbot
hsegment
soft
hemol
ecul
ar
axi
s.
Thequant
izedr
otat
ional
ener
gyl
evel
sfort
hisdi
atomi
car
e

Theener
gydiff
erencesbet
weentwor
otat
ional
lev
elsi
susual
l
yexpr
essedi
ncm-
1.Thewav
e
numbercor
respondingt
oagiven∆Ei
sgivenby

Ther
otat
ional
ener
gyl
evel
sofadi
atomi
cmol
ecul
ear
eshowni
nFi
gur
e39.

Fi
gur
e39:
Rot
ati
onal
ener
gyl
evel
sofar
igi
ddi
atomi
cmol
ecul
eandt
heal
l
owedt
ransi
ti
ons.

Thesel
ect
ionr
ulef
orar
otat
ional
transi
ti
oni
s,

Inaddit
iontot hi
sr equir
ement,themol ecul
ehastopossessadi pol
emoment .Asadipolar
molecul
er ot
ates,ther otat
ingdipol
econst i
tut
esthetr
ansit
iondipol
eoperat
orμ.Molecules
suchasHClandCOwi l
lshow rotat
ionalspect
rawhi
leH2,Cl
2a ndCO2 wi
l
lnot.Ther
otat
ional
spect
rum wi
l
lappearasf
oll
ows(
Figur
e40)
.

Fi
gur
e40:Rot
ati
onal
spectr
um ofari
giddi
atomi
c.Val
uesofBar
eincm-
1.Ty
pical
val
uesofB
i
ncm-1ar
e1.92118(
CO),10.593(
HCl)
,20.
956(HF)

Byusingr ot
ati
onalormi crowav
espectroscopy,ver yaccurat
ev aluesofbondl engths
canbeobt ai
ned.Forexampl e,i
nHCN,t heC-Hlengthis0. 106317±0. 000005nm andt heCN
bondlengthis0.115535±0. 000006nm.Thepr i
ncipl
eoft hemi crowaveov eninvol
vesheating
the molecul
esofwat erthrough hi
gh speed r
otati
onsi nduced bymi crowaves.The glass
contai
nercontai
ningwaterhowev err
emainscol
dsinceitdoesnotcont ainrotat
ingdipol
es.

Modul
e-I
V NMRSPECTROSCOPY(
TOOLSFORSTRUCTUREDETERMI
NATI
ON)

The1952NobelPr
izeinPhy
sicswasawardedtoFel
i
xBl och(
Stanfor
d)andEdwar
dM.
Pur
cell(
Har
vard)f
orthei
rdi
scover
iesr
elat
ingt
onuclearmagneti
cresonance.

I
. I
NTRODUCTI
ON: Nucl
ear magnet
icr
esonance (
NMR)
,a f
orm of
spect
roscopyt
hati
soneoft
hemostpower
fult
ool
sfort
hei
dent
if
icat
ionoff
unct
ional
gr
oupsandf
ort
hedet
ermi
nat
ionofconnect
ionsbet
weent
heat
omsi
nmol
ecul
es,
whi
chr
equi
resf
ort
hest
ruct
uredet
ermi
nat
ionofcompounds.NMRspect
roscopyi
s
ast
udyf
ori
nter
act
ionofener
gywi
thmat
terwher
eener
gyabsor
pti
onbymol
ecul
eswi
l
l
quant
it
atet
hathav
ebeenpl
acedi
nast
rongmagnet
icf
iel
d.
Thenucl
eiofcer
tai
nel
ement
s,i
ncl ng1Hnucl
udi ei(
pr ons)and13C(
ot car
bon-
13)nucl
ei,
behav
east
hought
heywer
emagnet
sspi
nni
ngaboutanaxi
s.Whenacompound
cont
aini
ngpr
otonsorcar
bon-
13nucl
eii
spl
acedi
nav
eryst
rongmagnet
icf
iel
dand
si
mul
taneousl
yir
radi
atedwi
thel
ect
romagnet
icener
gyoft
heappr
opr
iat
efr
equency
,
nucl
eioft
hecompoundabsor
bener
gyt
hroughapr
ocesscal
l
edmagnet
icr
esonance.
Theabsor
pti
onofener
gyi
squant
ized.

Agr
apht
hatshowst
hechar
act
eri
sti
cener
gyabsor
pti
onf
requenci
esandi
ntensi
ti
esf
or
asampl
einamagnet
icf
iel
discal
l
edanucl
earmagnet
icr
esonance(
NMR)spect
rum
(
Figur
e1)
.

1
Exampl
e: Thepr
oton(H)NMRspect
rum ofbr
omoet
hanei
sshownbel
ow.

Fi
gur
e1 MHz1HNMRspect
The300- rum ofbr
omoet
hane(
ethy
lbr
omi
de)
.

Fi
gur
e1Expl
anat
ion:
1. Thenumberofsi
gnal
sint
hespect
rum t
ell
sushow manydi
ff
erentset
sof
pr
otonst
her
e ar
eint
he mol
ecul
e.Ther et
e ar wo si
gnal
s ar
isi
ng f
rom t
wo
di
ff
erentset
sofpr
otons.Onesi
gnal(
consi
sti
ngoff
ourpeaks)i
sshowni
nbl
ue
andl
abel
ed(
a).Theot
hersi
gnal(
consi
sti
ngoft
hreepeaks)i
sinr
edandi
s
l
abel
ed(
b).Thesesi
gnal
sar
eshownt
wicei
nthef
igur
e,atasmal
l
erscal
eont
he
basel
i
ne spect
rum,and expanded and mov
ed t
othe l
eftabov
ethe base
spect
rum.t
hesi
gnalatt
hef
arr
ightoft
hespect
rum (
label
edTMS)
;itcomes
f
rom acompound(
tet
ramet
hyl
sil
ane)t
hatwasaddedt
othebr
omoet
hanet
o
cal
i
brat
etheposi
ti
onsoft
heot
hersi
gnal
s.
2. Theposi
ti
onoft
hesi
gnal
sint
hespect
rum al he x-
ongt axi
stel
l
susabout
t
hemagnet
icenv
ironmentofeachsetofpr
otonsar
isi
ngl
argel
yfr
om t
heel
ect
ron
densi
tyi
nthei
renv
ironment
.
3. Thear
eaundert
hesi
gnalt
ell
susabouthow manypr
otonst
her
ear
eint
he
 set
bei
ngmeasur
ed.
4. Themul
ti
pli
cit
y(orspl
i
tti
ngpat
ter
n)ofeachsi
gnalt
ell
susaboutt
henumber
of
prot
onsonat
omsadj
acentt
otheonewhosesi
gnali
sbei
ngmeasur
ed.I
n
br
omoet
hane,
si
gnal(
a)i
sspl
i
tint
oaquar
tetofpeaksbyt
het
hreepr
otonsofset
(
b),
andsi
gnal
(b)i
sspl
i
ti oat
nt ri
pletofpeaksbyt
het
wopr
otonsofset(
a).

I
I. BASI
CPRI
NCI
PLES:
1. Nucl earSpi
n:TheOrigi
noft
heSignal
Thenucl
eiofcert
ainisot
opespossessthequal
i
tyofspi
n,andt
her
efor
ethesenucl
ei
hav
espi
nquant
um number
s,desi edI
gnat .Thenucl
eusofor
dinar
yhy
drogen,1H,hasa
spi
nquant
um numberof1/
2,andi
tcanassumeei
theroft
wospi
nst
ates:+1/
2or-
1/2.
Thesecor
respondt
othemagnet
icmoment
s(m)al
l orI=1/
owedf 2,whi em =
char
+1/ m =-
2or 1/2..Ot
hernucl
eiwi
thspi
nquant sI=1/
um number e13C,19F,and31P.
2ar
Somenucl
ei,suchas12C,16O,and32S,hav
enospi
n(I=0)
,andt
hesenucl
eidonotgi
ve
anNMRspect
rum.Ot
hernucl
eihav
espi
nquant
um number
sgr
eat
ert
han1/
2.I
nour
t
reat
ment
her
e,howev
er,
wear
econcer
nedpr
imar
il
ywi
tht
hespect
rat
hatar
isef
rom 1H
13
andf
rom C,bot
hofwhi eI=1/
chhav 2.Si
ncet
hepr
otoni
sel
ect
ri
cal
l
ychar
ged,t
he
spi
nni
ngchar
gegener
atesat
inymagnet
icmoment
—onet
hatcoi
nci
deswi
tht
heaxi
sof
spi
n.Thi
sti
nymagnet
icmoment
giv
est
hespi
nni
ngpr
otonpr
oper
ti
esanal
ogoust
o
t
hoseofat
inybarmagnet
.

Fi
gur e2 1(a)The magnet i
cf iel
dassoci ated wit
h a spinni
ng proton.1(b)The
spinningprotonresemblesati
nybarmagnet .2(a)Int
heabsenceofamagnet icfieldt
he
magnet icmoment sofprotons( r
epresent edbyar r
ows)arer
andoml yor
iented.(b)When
anext ernalmagnet i
cfiel
d( B0)isappl ied,thepr ot
onsorientthemselves.Somear e
al
ignedwi t
ht heappli
edf i
eld( aspinst ate)andsomeagai nstit(bspinst ate).The
di
fferenceint henumberofpr otonsalignedwi t
handagainsttheappliedfieldi sver
y
smal
l
,buti
sobser
vabl
ewi
thanNMRspect
romet
er.

I
ntheabsenceofamagnet
icf
iel
d(Fi
g.2)
,themagnet
icmoment
soft
hepr
otonsofa
gi
vensampl
ear
erandoml
yor
ient
ed.Whenacompoundcont
aini
nghy
drogen(
andt
hus
pr
otons)i
spl
acedi
nanappl
i
edext
ernalmagnet
icf
iel
d,howev
er,
themagnet
icmoment
oft
hepr
otonsmayassumeoneoft
wo possi
bleor
ient
ati
onswi
thr
espectt
othe
ext
ernalmagnet
icf
iel
d(ot
heror
ient
ati
onsar
edi
sal
l
owedont
hebasi
sofquant
um
mechani
cs)
.Themagnet
icmomentoft
hepr
otonmaybeal
i
gned“
wit
h”t
heext
ernal
f
iel
d or“
agai
nst
”it(
Fig.2)
.Theseal
i
gnment
scor
respond t
othet
wo spi
n st
ates
ment
ionedear
li
er.
Thet
woal
i
gnment
soft
hepr
oton’
smagnet
icmomenti
nanext
ernalf
iel
dar
enotof
equal
ener
gy.Whent
hepr
oton’
smagnet
icmomenti
sal
i
gnedwi
tht
hemagnet
icf
iel
d,i
ts
ener
gyi
slowert
hanwheni
tisal
i
gnedagai
nstt
hemagnet
icf
iel
d.Thel
owerener
gy
st
atei
ssl
i
ght
lymor
epopul
atedi
nthegr
oundst
ate.
Ener
gyi
srequi
redt
o“f
li
p”t
hepr
oton’
smagnet
icmomentf
rom i
tsl
owerener
gyst
ate
(
wit
hthef
iel
d)t
oit
shi
gherener
gyst
ate(
agai
nstt
hef
iel
d).I
nanNMRspect
romet
ert
his
ener
gyi
ssuppl
i
edbyel
ect
romagnet
icr
adi
ati
oni
ntheRF(
radi
ofr
equency
)regi
on.When
t
his ener
gy absor
pti
on occur
s,t
he nucl
eiar
e sai
dto be i
nresonance wi
tht
he
el
ect
romagnet
icr
adi
ati
on.
Theener
gyr
equi
redt
oexci
tet
hepr
otoni
spr
opor
ti
onalt
othest
rengt
hoft
hemagnet
ic
f
iel
d(Fi
g.3)
.Onecanshowbyr
elat
ivel
ysi
mpl
ecal
cul
ati
onst
hat
,inamagnet
icf
iel
dof
appr
oxi
mat
ely7.
04t
esl
a,f
orexampl
e,el
ect
romagnet
icr
adi
atonof300x106cy
i clesper
second(
300MHz)suppl
i
est
hecor
rectamountofener
gyf
orpr
otons.
Figure3 Theenergydiffer
encebet weenthet wospinst at
esofaprot ondependson
thestrengthoftheappliedexternalmagnet icf
ield,B0.(
a)Ifthereisnoappliedf i
eld(
B0=
0),thereisnoener gydiff
erencebet weent hetwost at
es.(b)IfB01.
41t esl
a,theenergy
6
diff
erencecorrespondstot hatofelectromagnet icradi
ati
onof60x10Hz( 60MHz) .(c)
Inamagnet i
cf i
eldofappr oximately7. 04tesla,theenergydi f
fer
encecor respondst o
6
electr
omagnet i
cradiat
ionof300x10Hz( 300MHz) .

Therel
ati
onshi
pbetweenthef r
equencyoft her
adi
ation(ν)andthest
rengt
hoft he
magnet
icfi
eld(
B0)i
sν=γB0/2π;wher eγi
sthemagnetogy
ric(
orgyr
omagnet
ic)r
ati
o.
Forapr
oton,γ=26.
753rads-1t
esla-1.

I
II
. NMR 
Spect
romet
ers:

MostNMRspect
romet
ersusesuper
conduct
ingmagnet
sthathav
ever
yhi
ghmagnet
ic
f
iel
dst
rengt
hs.Super
conduct
ingmagnet
soper
atei
nabat
hofl
i
qui
dhel
i
um at-
270°
C
andt
heyhav
emagnet
icf
iel
dst
rengt
hsmor
ethan100,
000t
imesasst
rongasEar
th’
s
magnet
icf
iel
d.

400 MHz Super conduct

ing
MagnetofanNMRLabor at
oryat
Depart
ment of Chemi
stry
,BI T
Mesra,Ranchi

Fi
gur
e4Pr
inci
ple&Di
agr
am ofaFour
iert
ransf
orm NMRspect
romet
er

Cer
tai
nnucl
eii
nthepr
esenceofamagnet
icf
iel
dbehav
east
hought
heywer
eti
nybar
magnet
sthatal
i
gnt
hemsel
veswi
thoragai
nst
theappl
i
edmagnet
icf
iel
d.Thenucl
ei
spi
n(pr
ecess)aboutt
hespect
romet
er’
smagnet
icf
iel
daxi
s(t
he“
appl
i
ed”magnet
ic
f
iel
d),mucht
hesamewayt
hataspi
nni
ngt
opgy
rat
esar
oundt
heaxi
sofgr
avi
ty.The
pr
ecessi
onalf
requencyofeachnucl
eusi
sdi
rect
lyr
elat
edt
oit
schemi
calshi
ft
.Wecan
i
l
lust
rat
eanucl
earmagnet
icmomentpr
ecessi
ngaboutt
heaxi
sofanappl
i
edmagnet
ic
f
iel
d(B0)usi
ngav
ect
orr
epr
esent
ati
on,asshowni
nFi
g.5.
Appl
yi
ngapul
seofr
adi
o
f
requencyener
gyt
hatmat
chest
hepr
ecessi
onalf
requency
oft
henucl
earmagnet
ic
momentcausest
he magnet
icv
ect
oroft
he nucl
eust
oti
p away
from t
he appl
i
ed
magnet
icf
iel
daxi
s(hez-
t axi
s)t
owar
dthex–ypl
ane(
Fig.5)
.Thenucl
earmagnet
ic
v
ect
orst
il
lpr hez-
ecessesaboutt axi
s,buti
tli
esi
nthex–ypl
ane.Fr
omt
heper
spect
ive
ofat
inycoi
lofwi
re(
cal
l
edar
ecei
vercoi
l
)si
tuat
ednextt
othex–ypl
ane,
rot
ati
onoft
his
v
ect
orar hez-
oundt axi
sbuti
nthex–ypl
anepr
esent
sanosci
l
lat
ingmagnet
icf
iel
dtot
he
r
ecei
vercoi
l
.Andj
ustaswi
thl
arge-
scal
eel
ect
ri
calgener
ator
s,t
hisosci
l
lat
ingmagnet
ic
f
iel
dinducesanosci
l
lat
ingel
ect
ri
ccur
renti
nthecoi
l(Fi
g.5)
.

Fi
gur
e5. Or
igi
noft
heSi
gnal
inFTNMRSpect
roscopy
.
Thi
scur
renti
sthesi
gnal
det
ect
edbyt
heNMRspect
romet
er.

Thi
sener
gycomesf
romar
adi
ofr
equencypul
segener
atedbyt
heNMRspect
romet
er.I
n
amat
terofsecondsor
less,howev
er,t
henucl
eusr
eleasest
heener
gyi
tabsor
bedback
t
othesampl
eenv
ironment
,r
etur
ningt
henucl
eust
oit
sgr
oundst
ateener
gyasi
tmov
es
backt
owar
dthez-
axi
s.Asi
tdoesso,
thev
ect
orcomponentofmagnet
izat
ioni
nthex–y
axi
s di
mini
shes,and t
heobser
ved el
ect
ri
calsi
gnaldecay
s(Fi
g.5)
.The osci
l
lat
ing
el
ect
ri
calsi
gnalpr
oducedby
theexci
tednucl
eusi
sther
efor
enotasi
gnalofst
eady
ampl
i
tude,butonet
hatdi
esaway
exponent
ial
l
y.Thi
ssi
gnali
scal
l
edaf
reei
nduct
ion
decay(
FID)
.TheNMR comput
erappl
i
esamat
hemat
icaloper
ati
oncal
l
ed aFour
ier
t
ransf
ormt
oconv
ertt
hesi
gnalf
rom at
imev
ersusampl
i
tudesi
gnal(
theFI
D)t
oa
f
requencyv
ersusampl
i
tudesi
gnal
(theNMRspect
rum t
hatwei
nter
pret
,Fi
g.5)
.

As we ment
ioned,t
he chemi
calshi
ftofan NMR si
gnali
s di
rect
lyr
elat
ed t
oit
s
pr
ecessi
onal
fr
equency
.Si
ncemostcompoundshav
enucl
eii
nav
ari
etyofenv
ironment
s,
t
hey
hav
enucl
eit
hatpr
ecessatav
ari
etyoff
requenci
es,
andt
her
efor
eexhi
bitsi
gnal
sat
av
ari
ety
ofchemi
calshi
ft
s.TheFI
Dsi
gnaldet
ect
edbyt
heNMRspect
romet
eri
san
aggr
egat
eof
alloft
hesef
requenci
es.Apower
fulaspectoft
heFour
iert
ransf
orm(
FT)
,
asamat
hemat
ical
process,i
sthati
text
ract
sthesecombi
nedf
requenci
esf
rom t
heFI
D
andconv
ert
sthemt
odi
scr
etesi
gnal
sthatwecani
nter
preti
nanNMRspect
rum.
I
V. TheChemi calShi
ft
,PPM andt
heδ-
Scal
e
Al
lpr
otonsdonotabsorbatt
hesamechemicalshi
ft(
δ)i
nanext
ernalmagnet
icf
iel
d.
Thechemi
calshi
ftofagi
venpr
otoni
sdependentoni
tschemi
calenv
ironment
.Theδ
v
aluet
hatwer
epor
tforapr
oton’
schemi
calshi
fti
sact
ual
l
yameasur
eofi
tsNMR
absor
pti
onf
requency
,whi
chi
spr
opor
ti
onalt
otheext
ernalmagnet
icf
iel
d st
rengt
h.
Smal
l
erchemi
calshi
ft(
δ)v
aluescor
respondwi
thl
owerabsor
pti
onf
requency
.Lar
ger
chemi
calshi
ft(
δ)v
aluescor
respondwi
thhi
gherabsor
pti
onf
requency
.Chemi
calshi
ft
s
ar
e mostof
ten r
epor
ted i
nref
erence t
othe absor
pti
on oft
he pr
otonsofTMS
(
tet
ramet
hyl
sil
ane)
,whi
chi
sdef
inedaszer
oont
heδscal
e.Asmal
lamountof
TMSi
s
ei
ther i
ncl
uded as an i
nter
nalst
andar
dint
he sol
vent f
or a sampl
e,or t
he
NMRspect
romet
er i
tsel
f i
s cal
i
brat
ed el
ect
roni
cal
l
y t
o a chemi
cal shi
ft
st
andar
d.Si
(CH3)
4Tet
ramet
hyl
sil
ane(
TMS)
Thesi
gnal
from TMSdef
ineszer
oppm ont
hechemi
cal
shi
ft(
δ)scal
e.

Tet
ramet
hyl
sil
anewaschosenasar
efer
encecompoundf
orsev
eralr
easons.I
thas12
equi
val
enthy
drogenat
oms,
and,
ther
efor
e,av
erysmal
lamountofTMSgi
vesar
elat
ivel
y
l
argesi
gnal
.Becauset
hehy
drogenat
omsar
eal
lequi
val
ent
,theygi
veasi
ngl
esi
gnal
.
Si
ncesi
l
iconi
slessel
ect
ronegat
ivet
hancar
bon,t
hepr
otonsofTMSar
einr
egi
onsof
hi
gh el
ect
ron densi
ty.Theyar
e,as a r
esul
t,hi
ghl
yshi
elded,and t
he si
gnalf
rom
TMSoccur
sinar
egi
onoft
hespect
rum wher
efewot
herhy
drogenat
omsabsor
b.Thus,
t
hei
rsi
gnal sel
dom i
nter
fer
es wi
th t
he si
gnal
s f
rom ot
her hy
drogen at
oms.
Tet
ramet
hyl
sil
ane,
l
ikeanal
kane,i
srel
ati
vel
yiner
t.I
tisal
sov
olat
il
e,hav
ingaboi
l
ing
poi
ntof278C.Af
ter
thespect
rum hasbeendet
ermi
ned,
theTMScanber
emov
edf
rom
t
hesampl
eeasi
l
yby
evapor
ati
on.

The chemi
calshi
ftofa pr
oton,when expr
essed i
n her
tz(
Hz)
,is pr
opor
ti
onalt
o
t
hest
rengt
hoft
heext
ernalmagnet
icf
iel
d.Si
ncespect
romet
erswi
thdi
ff
erentmagnet
ic
f
iel
dst
rengt
hsar
ecommonl
yused,i
tisdesi
rabl
etoexpr
esschemi
calshi
ft
sinaf
orm
t
hati
sindependentoft
hest
rengt
hoft
heext
ernalf
iel
d.Thi
scanbedoneeasi
l
yby
di
vi
dingt
hechemi
calshi
ftbyt
hef
requencyoft
hespect
romet
er,wi
thbot
hnumer
ator
anddenomi
nat
oroft
hef
ract
ionexpr
essedi
nfr
equencyuni
ts(
her
tz)
.Si
ncechemi
cal
shi
ft
sar
eal
way
sver
ysmal
l(t
ypi
cal
l
y<5000Hz)compar
edwi
tht
het
otalf
iel
dst
rengt
h
(
commonl
ytheequi
v entof60,300,or600mi
al l
li
onher
tz)
,iti
sconv
eni
entt
oex
press
t
hesef
ract
ionsi
nuni
tsofpar
tspermi
l
li
on(
ppm)
.Thi
sist
heor
igi
noft
hedel
tascal
efor
t
heexpr
essi
onof
chemi
cal
shi
ft
srel
ati
vet
oTMS:

Forexample,
thechemi
calshif
tforbenzenepr
otonsi
s2181Hzwhent
hei
nst
rument
i
soperat
ingat300MHz.Therefor
e,

Thechemi
cal
shi
ftofbenzenepr
otonsi
na60-
MHzi
nst
rumenti
s436Hz:

Thus,
thechemi
cal
shi
ftexpr
essedi
nppm i
sthesamewhet
hermeasur
edwi
than
i
nst
rument
oper
ati
ngat300or60MHz(
oranyot
herf
iel
dst
rengt
h).

VExamplesofStr
uctur
eEluci
dat
ionthr
ough1HNMRSpect rum
Example1:
The300-MHz1HNMRspect r
um ofacompoundwit
ht hef
ormulaCH3CH2CH2Br
.
Expansi
onsoft
hesignal
sareshownintheoff
setpl
ots.

Exampl
e2: Et
hanol

Exampl
e3: 1,
4-di
emt
hyl
benzene
Refer
enceBook:
i) Organi
cChemistr
y:Sol
omons,
Fry
hle,
Sny
der
,11e i
i
) Spect
roscopy of
Organi
cCompoundsbyP.S.Kal
si;
6thedi
ti
on