Raman Speckoscop T

and
deals wih Scattounq
ot light ard
Kaman
NAman Specbrosco ps Is - v
not wiJh its absorptions 32
hamogenous mateia Sueh qas,
as

heory When a
is exposed. to a beam
solid.
diquud tranupaHent
OY

dight most of h e paut of it is

O mono chromatic
Of is called
SCattoued. wihout achange in wavelena*h . This
Rayleigh Scatteunsi
Raman observed a t inhe sca-
Howeve
wavelengh
weak radiations of diffeuent
tteued dight alkeuation in
also present This
OY hrequenag wee
obseaved by C.V
trequen i Called Ranan Effee
Ranan i n 1928 he Mest Commony wed
is "He-Ne
wh he wavelengh ot incidet ligh as 3628A
Soce
SOwnce
AP he kineic enegy of he photon and
he
mole Cle remains unchanged 0 besore and afte
ot ConseHvaHon ot
Clision hen trom h e uaw
ene E+mv+h = E'+m+h'
a
2

E+h =E+h
photon a hy' is eneg he
b is Enexgu oincident
afteu collsion.
of scattened photon
(rotakional, vibrattonal
ieleehvonic
s enexgu ot
betore
molecCule
collision

mole cuwla eneugy odte Colloision

E is he

E-E hh
E-E=
-
Raman hcquen
OY
=
A itis known as Raman shft.
Diffeuence between he trequen ot he inci dent ligkt
and hat of pauticulan Scatteled line is Constant
and depends on upon he natwe of he Suhstance

21
 which is iradiakcd.. TH is completely independant
bh e chaactouis
he reouen ot incide nt lght tic t Scattung susb
i f h e Sanple was exutcd by-he 43s8 A
line of meH CL A kaman 1ine was obseAved
at 4y47A .Calculate Raman shift. Inc)
A = Vo- VR E= h freae
E hC

R -
H59Cm'
AV 4358 X1cm
yu47X16Cm

22481Cm = S9Cm
22446 cm

=Stokes line.
Stoke's and Antistoke's line A smal frackion
is scatteued. due to collisions
ot inident light
scattttex and photon s
between moleules of he tomed
i s asSumedhat a Complex is
of light
between a mole cule and a pheton duwun veuy
inteuval (ioSsec) dt cellision. Tkmecales
Short
Ouse
will
he collision is elastic,he complex
1) TF mo le Cule o
same
photom
disso ciate to givehe Scatteued
enetg which iE had betore CollisionSo,
enegy'aX inuden
Photon will have he same
of unmo di'fied
Photon ueads to appeanance
ihes known as Rayleigh ScattCung.
AV Oo E E
No Changen Ws Cake me lecule attex absor bin
ene
gets excited to highen utstable
Inident radi ation
vibratto nal State from hich it Tetns to the
Orginal stateate eitting the radiaions
Sla freuencs
 h h
h
h h
b

-E E
AV

Eo Eo Anistokes lines
Stokes lines Rayleiq
-= AV0 scatoun
>.E,9E2 A=0
E E
=
EE E = E afte
Molee bekore
oleu bekone hene
Case L Af he collision is inelastic between
feH ot ene between
o r trans
willbe exhange and he inudent photon.
Moleude
he SCatteuing uy aise
dutfenent Case
Two awau
Collides 2 e n e g is taken
i When he pheton retuens to"
retwans to
I h his case molecules
daeh e moleCule, sBaBe aftou excitation rom hee
di'ffeuent vibyatonal
he mole
state. cule hus emuts
round VI braional
round
han h e inuden
Yadiations wih a dewen treauency
light Such Raman Scattehed 1fnes which aue Called
O bsex vea. in he Small hreauency side aHe
Stokes ines Hadiationfrom
Collides h e mole cules
hen h e photon eteCLles n Ws
i he enegy Ss dtetttot
tel from Hrst exited
Case moledele iSprome viraktonal stake
unstable vibraklonal stake
vibraional State to highe tto
by e absovtion ofadatton CoresPon ding
moleculeshus emits Thdiaion
d freguenUyV The Scattoed.
hequeny Sueh Raman
with higHe
kndwn as Ani stokes lines.
ine aHe

transteued from molecule to radiation 23

 Stoke's lines aue more intense han antistoke's lines
CausedL by meleules
The
he reason is hat Stokes lines aHe
Ot lowe enegy leve whidh is moree Populatcd
P opuat and.
have mOre intensity off
o
absorption Antistokes lines
level
aue causes by moleces af hghen eneg
which QHe 1&s Po pulaed ahence less intence.
les&han One pain lo6 of in ident
ight undergoe inelastic satteuing. Ranan lines
aHe weak,.

Rayleigh lines > Stokes Antistokes

A+ room tenp. he no. of mole cules posseaing.
low enegy IS more so stoke's transitHona aHe
more freadenF Intonse. bu when he tcnp. is
raseda he kinetc enea ofhe mole cule incrases
and anhstokes li'nes qredually incrtases.
Citoua l dassical heory hen a molecule show perio du'c
Change in polarizability due to its vibrahional Or
Totaional Oscillation CPotoiebiltyde te ttsibratienal
torad h e ease wih hich he eCloud aLDUnd
otationad
_ mole cule Can be distorted) /Polau'sed
The elechic feld EasSociaked wh elechomagneic
Yadiaion nduces a dipole memeak olele.
in he Moleule
JG- E

mole cwlan vibration does not Change d

totation

To be Raman Active £ o

he molecule must poss anr'sotropic Polausability

which should change dwing moleclan rotation OY
vibvation fov vibrdtional or rotational-vi brational Raman
Spechra Anisotopic polasability depends upon orientaion
of he moleCule
is
In he Case otan abomhe polai sability
isoropic beeause same distoYtion is indued wtateve
 he drection of he applied iela. Tn Case of molele
he extcnt of distortion Y Polasisabity is isebopic..
change whhe direction of fteld
ma Ca Excusion Rule- Suh
Mutualmolecules wke datomi
as
For
FoY Centrosymmebic
molecules ike Co, which
H2 0 ) N2 e t and inea
h e vibrabionu which
Posses Centte otSymmeby
known
CUHe IR inackive ane Ramai ative. Tkis is
mutual
utual exclusion rule. CaHa hence R Raman
Oe COmpli menkau
for eq HH 3N-S
3N =|fundamental vibrabions
3x2-S
rise
Vibrational modes which aHe IR inautive may re

to obsexvable bands in Raman Specta- Ramann

o Symmeic x chargeîm
CO2 Polasibi
Asgmmcbi
1,2 dichloro O-0-Bending
ehene
HO The moleules for
whith Cos is
S02 Cis isome trans
aakye No change in dipole,
momenk| abseat Can
NO COS beIR a wellas
IRaehve Ramanaaive QRanan ashive.
inten
degree of polau. sahonCui) he
Parametens A 4he Shape othe
Civ)he
width
sity
Sity
anlineaines. H RARAMN
Roman N , O N N - o BoTH

Raman ative
2 IR inautive RRANAN Bo1
CS
Rotaional Speca
ot diatonic mølecules ( Pne Rota-
tHonal Raman
h8n2Ic Ei,-h T(T+1)
8 M
Fu BJ(J+I) Fu he
transiton Ao+ Change in polauability
u For
along intcAnulclean axis
aller for r o tattonal Raman spechg,
Lii) SeleeHon rles Cfull) he polauigability
Totation
Snce on eneg
of molecule etwn
ene to its
Initial Value twice

h e seleaion rule is is (A5

 AT=0 ,E2 AJ O RayleighScaktuun
AJ t2 Raman lines
- stokes lines
A - Anti stokes lines
Av -
T ,1, 2,3
F (T+1)
3 4
12
J 20B
0 28 6 12

E
y+2
BCT+2) CT+3) - 8JTH)
AT=+2 B LcI+2) CJ+3) - JT+I)J

BLT 23+6+3T-3+J]
Vjt2
6
lo B
14 B
2-0B

128

6 2

2
O
4B4B-4-66 6EqFuB

6B
L L
48 6
AJ 2 Stokes
AJ =
+2 ani stokes
Moleculau Polaisation ' When a molecule is put
in to a static elecic ield, i t Suffes some

distorti The
The positively chaged nuulei qets
adtraeted towads negathve pote and es to positive
Pole
he sepetation of chae centc Cases Ond
in duced elesic dipole moment be se in hemale
Cule Phenamenon is callea PolanisaHon.
Combininq both io Raman Shift
= t B(YT+6
AT=o

68
4B
48 HB 68

Ag = 4+2
AT -2
Stokes
Rayleigh Antistokes

TR Vs Koman
lines ane
incident
indcpendent ot frea ot vis
1Raman region
radiation so Can be easily studied in
is obthined in IR range
hile 1R Spechra
is prcsence
not inteuleued by
2.) Roman spechra
Roman
Sample sheue a s \R
ot moistute OY H2O in
of watex.
afected by Prsence
is
b cam be obtained easiy in
in
Raman Speera
3) qaseous iquid and Solid State of copovnd.

4) Raman Scatteing
Absor phon lau
 Ranan Specto scopy

wha is polauzakion ?

A Polauzaion
Eleckric chauge
H H
X

d/u E
LPolaisakibity
o u d i p o l e momen

cleud aeund
wNh which thee
he ease
Can be distorted )
aa mole cule to
for a
tor a Compound
What is he crituia
be Raman aive
To be o
A
Kaman autive

mole Cule must PossesS anisotropic

The should change duinq
dwing
moleuan
m oleuan
kich
Polcusab1l1ty must be"
be Some
vibradionTheue
otation or
O
pola sabil1 ty
.

Change s
H H leeic field of
ele chro magnetiC
Tadi ation
es
distortion tans

Ht C B N2 ,02, CH4, CGH

HF HBr) HL CH
CO Sy mmehric Shreng
 Exdusion Priniple
Muthal
IR and Raman Specha Supplement eaeh
A
o4he tor h e delc mnatioo otmole Cla
Shucd we a molemle has Cenre ot
Symmet hen inhartd in aetire vibrationa!
mbdes C e Raman aH ve and VIce vense
for e CO
Dipole moment Polauzability )
Symmebmcal chreëh RAMAN

C 0
O RinauhiMe YES ATE
NO
Asymmchical Shttch e s
RAdh Rama
Jnacive

O=C=o

Seleetion ule tov

Gure
)Vibrakional Ra man
ii) Rotakional Raman
Selechioo rule
for vibrationa Raman

AV
A 0 tnhictokes

for Rotational Raman

fo
A - 2 stokes

=+AV
Stoke
a -

A)
-A anHstoke
= + Av
VR-PoTAY
 exuttd by 13S8 A line of
A sample was

mexy A Raman line obseeved at

was

y441 A Chlclate h e Raman shiBt (incm)

of inudent photon)
A Guven V Chequency
= 22946 Cm
4358lo °cm
scatcued photon ving Raman
af
Chreaue7 line)
Cequency
22487 Cm
-
A qyy7X10 Cm
22946-2R487 Cm

h A 45Cm
V e V i i s stoke's ines
E

wawelengdh yX1o*A Jhe

ot Spaeing ot
Hadiation
. Using aa
firststoke's line Rayleigh
appe ans line Calulate
350Cm romhe
na n i sstoke
tokes line in
in
of H s f
he
h e tcauency
wave umbeH

AY
=
3So cm 5000 Cm
A
xio°xlo Cm
+AV Stoke's
=
R anhstoke
- AY

+AVF RSo00+ 3So

Ve= 253SoCm
 Showhe Syatems ate Raman aetve OL

IR aive
dipole momenk
A (1 14N 5 N Change in
d u e to Osymmedc

Streeking IR

n Ehulene
C=C Streehing
( Zene dipole moment

in polau
But change
Zabillty
RAMAN ACTVE

(3 C-o Sheedng in Acekone

Change i n dipoemoment

TR ACTVE)
- Change in polaxizability
RAMAN ACTIVES

(1 Re-Re Sheehing in
NO
Change r

(Co)Re- ReCco)s
(Co) di pole momenk
BUT
Changein Polaxizabl)ly

RANAN ACTIVE
 Table Ta-1. Difference between Infra-red and Raman spectra

Infra-red spectra Raman spectra

1. It is due to absorption of a radiation 1. It is due to the scattering of radiation

by vibrating molecules.
by the vibrating molecules.
2. The dipole moment of the molecule 2. The polarisability of the molecule changes.
changes. 3. The intensity of Raman line depends
3. The intensity of IR absorption band
magnitude of the change of
depends upon the magnitude of the upon the
change in dipole moment of the molecule. polarisability of the molecule.
4. Water can be used as solvent.
4. Water cannot be used as it is opaque
to IR.
5. Dilute solutions are generally used. 5. Concentrated solutions are used to
increase the intensity of Raman lines.
6. Optical systems are made up of special 6. Optical systems are made up of glass
or quartz.
crystals like NaBr, CaF, etc.

414 Structure Elucidation by Raman Spectroscopy

Raman spectroscopy is of great value for molecular vibrations that are inactive in the infrared
due to molecular symmetry. For centro-symmetric molecules like H,, CO,, CH, ete, the vibrations
which are IR inactive are Raman active In fact, Raman spectroscopy supplements infra-red
the
spectroscopy. It is an important tool for solving some intricate research problems concerning
structure elucidation of compounds. Some important applications of Raman spectra in structure
elucidation are:
Structure of centro-symmetric molecules. Carbon dioxide is a centro-symmetric molecule
with linear structure (O = C 0). One expects two fundamental modes in the infra-red and one
in the Raman. Actually, it is confirmed experimentally. () 1337 cm (Raman active) and (i) 667
cm (ii) 2349 cm which are infrared active. The structure is said to be centrosymmetric when
the vibration is infrared active and Raman inactive and vice versa.
i ) Structure of N,O. If N,O is symmetrical like CO, one should expect similar behaviour
as seen in carbon dioxide. If it is unsymmetrical as N - N - 0, then vibration should be active

both in infrared as well as Raman.

Actually, additional fundamental vibration is observed both in IR and Raman spectroscopy.
This shows that the structure of N,O is N - N - 0.

(ii) Structure of water. For water to have bent structure, the fundamental vibrations v,v, and
V should be active both in Raman as well as in IR. Since, it is experimantally true, water has a
bent structure.
(iv) Structure of Mercurous salts. The Raman spectrum of the aqueous solution of mercurous
Salt shows a line which is absent in the spectra of other metal nitrates. The two shows Hg - Hg
covalant bond in Hg molecules.
(v) Structure of Chloro Complexes of Mercury. The Raman Spectrum of a solution of
HgCl, and NH,CI mixed in the ratio of 1:2 shows a strong line at 269 cm". This compares with
a strong line at 273cm for solid ammonium tetrachloro mercurate (D showing the formation ot
HgC1 in solution.
(vi) Hydrogen cyanide. Raman spectrum for hydrogen cyanide shows two lines 2062
It can be attributed to two Isomers in
at cn
dynamic equilibrium.
 HH IR iaukive Rautive F2, u2, Br , Na,0
IR Active R auive HBr, HI
HF ,
R inactive Rauhive
Cl-U
IR RAMAN
asymmeic shrechinq Acti ve Anachve
*C0 Symmchric Sbeeking AnauHve Achve
Active Anachive
ben ding
H20 Symmehic RAMAN
PRCHve Achive
As mmehic AcHve Achvc
Bending Acive AtHve
R RAMAN
ONF N-O She AcHve Acive
N-F Srec" Anhve AChve
0-N-F bendinq AcHve Acive

cs IR2 RANAN
R 4 RAMAN BOTH
NH3 NO 1RRANAN
CSymmeic
Asymmeic S0
Scissorin
wa IR RAMAN BOTH
HCN RAMAN BOTH
R
Cocs
Csttehing, bending )
Ramam active (Summehical
Chy , seehi
al
IR aatve Casymmehic sheehing
Bendin
CM Raman aerve (symmehic sbeeing C-H,C-)
H-CEC-H C-C-H Bending
R aeive other dike, Asummehic uaa
Cis CH IR Raman boh astive aeive
inacthve buC Raman
trons CaMC Mostly R
Cenhe ot Symmeby)

Roman 4 R boh