Rotational Spechrosco p At involves he branaitiona between

he
h e Hotational enegy devels ot a gaseous malecules
havin
Naving pemanen dfsole momend On he absorption of
radiolions fallng in h e spechra a g e d - l o o c m
Cmucrowave siegton also known as iCYowave Spectroscopy.
( inits tumblinq moleude in qas
tree to rotate uhideed )
why Orly qaseosmolecules ?
tor molecules in solid 2 diqpid.
tree Totdtion is not possible
inteumolecla torce Kotation about each unigue
State due to
axis 1s aAsociated. wih a Se of quanized. Cdiscrtte)
moment ot inetia
enetg levels dependent on he
abou hat axis and a 9uantum no. Jn solid a diqud
hese Hotational eneg devels ane not
quantised

Princple peHmanent dipole mament

A molecule
Osci
t1atng
tield byrotation uhen
generates osetuetraieg eledhic
othe melele becomes
he fregqueny ot rotahon
egua Keaueny ot elechic tield ot radiatton,
to he otesonance and
heue Ocu ahephenomenon
hence enegy Can be transfeu-ed tromhe radiation
tohe malele &shous absorption specha or
Vice veRsa.
7Hadiation
Microwoave Active molecules. having
momen e Hu, Co, CN.
PeHmanent dipole
Homo H2 N2 O
ucrowave anaeive molecules
Helexo -

having. COS
H H-C=C-H
e Cts
-u

Divcehion
ot dipole
Veutical
Conponen
G

dipole
1me
(14)
 -S

elecknc Held rotatcs dipole mamen

Change
in yele"[seeondL
Aadiation eleehic Held
of-atatton
eleeic D
fietd
magnitude
Uadius Chavge
deesnot
but its a veetor quahty Charge
So dieetion changes
0
+6 H H-u
H H C
+

Cone
totabtonal values ane quanisea
devel to anohe devel
Rotaking
nea4 Symmetric
o p
Spherical
eSphenical
Asy OP
Asymmehrie

-Cen H
otgTaiky H
h SH h

TAATAT
ánaghive
T TcTA No dipole
Prolakt momen

15
Rotahional Speabra otDiatomic molecules
Mbondlengdh.
Assuanq a diatormie moleule AB behaves
Qs a ugid roto, t means intcunuean
bond distance daes not change during mA
Hotation A
mA ma - masse of atom
distances ofatom
from Cenhe of ravit
at cete ot ravitu
mA HA mgHB
H U-A

hu A A meCH-uA) = mAt - meMA

mAtmB ) t A = m g

A mg SotA mAU
mATMB mATMB
Moment at ineia ot diaBomic molecule
2
L mAHA"+ mgHe
2
+ m B m A M

mAtm

2
mem
(matmB
2
mAm
(mAtmnB m

s ot iakomic molecle
whee Hedueed mas

J mA MB
mAtB

6
angula momentum of
uotaing L I C
meleJe angula
memenk-att velotib
ineia
Encgy t otabing, me lecule Ej, - T

Angulan velocity
2 it can integral
have
Rotational quantum no.

Vaues trom zevo Onwands 0, ,3,3...

h a t deteumines angulan
Ca vector quantum
no.

molecwle rotaingdboub
momenkum o a
an axishrough its centen af Wass)

L TL7-) h Jo,1, 2,3

momentum is 9.uantised
angula

RI
h T ( J + ) Joule
h TlJ+1)
E 8I
(2T)x 2T
hTJH)|
h2 Joules
hich
in c m unts
aso be expressed
The eneg
Can
as
rotational tetm F(I)
IS normally
reported
AE = h
AE h
AE hC
CCm)
TlT+I) Cm
8n2I hnc
h JlT+H) Cm
Fu 8nIC 8 Rotational Comstant

8n21c

BJC JH) Cm
 the vaues ot J= o, 2 -- , *he aulawed
Pting
Puthing a diatOmic molecLe
levels o
Totational
enea
enengy

2 | 3 56
J S6B
128 20 30 128
28
FCJ) -8J LJH)cm
FCT) = Bx1l1+1)
28 Cfor TI)
b/w the rot"e
for radiative transihion
Selection rule di akomic molewle
devel for a uigi d
AT =+E emission
c
A J = +| 4
tOr ahs0Tption ot HadiaHon
radiakion AJ = CI+1)
BCT+)CT+2)- BT
Fg+1)TJ B La+33+ 2
-J]
8 CT+1) cm"
=B(+1)(1+2) - B(o)lo+1) V--2 4 8
3B- B

V23 6 B 28
These ines ae eualU Spaced by amt of
ha
Appeanance ot rotationa Spec - 30B
A 2BJI)
otaton 20
Since many ot he dowe
evels ate populatta , it
is expec-
hmat pune Tot" spechum wouwld
ted
move
absorption 3
an one -128
Comsist
spaeing ane
line AHHhaughhe -6B
intensi tiel of
eal but he
a hese transitions aHe not 2B
No ot melecles
eaual
Prom Oted trom qiven level J=o T
depends on its Populabion (N/) ie daxgexhe poe
molecules t a t be promoted to
age he no of
can

of ahsorpion
mext highen level hencelangen
next
he intonaity
3B

128
Dekcumi nahHon of Bondlegdh.
2 6B

- h 2B
8nIc
126
h82BC 8 48 68 8B lo6

I - uHA
h 3
H
8KBcu
= inteunucleas distance

is 13A. Cal e inJLin

nutctea distance of Co
Anto
of moleCle in SE
ev and nqulan velocity.
excited rotdtional deve
a mas s
6 2 66 x l62k
= 113 xlo m
= 1 4 x1o
mtm 2
I
6 ka,m
JC+I) J-l h
E h 42I
8I

= (6-626 x l634)Ts T61xIo

92 C146x166 kgm
4.16 xlo e v
lev 6 xto1J
2 3-2-3xtoHadianN

I*
E
(19
 Ene otrotation BT CTH) cm
wheue 8 Totational conatant
T TOotabionas 9uanb no
AE = Ei+
= 28(J+1) cm
2B 28
Selection Tule HB 6B 86 loB 12
tI absorpioo6 2B

-| e ssion
*Rotational Spechra aHe obseved in Gaseous state
blc he Hotational enegH devels aHe not qjuantised
in solid a
iquid stateatse in 9ases rotation
in al ireetion is possible.
OP
Tso tic etfcet CRotaiona Speta)
D

mtm 2 Tou H u spauing bl

B h
8-IC BDu BHu lines

E - BJIH) E pu Enu
ie Onn Heplauinghe H nom ils isotope enexgy
decreased
J 3
J 2

JI T-0
J=d
Spaing get decra
Mole cula, decrased
why daqe have losey spaced
Totaona ene4 levels?
Spaeing 28 h
Applicahons ot Rotational Speckra
of polan molecule.
DetcH mination of bond length
of Symmetuy of molecule.
2 Detex mination
moment
3. Dete nation ot dipole
Shift of rotational frequenc
A
dipole moment
d
E ExteHnal eleehdc Held
AD< CdxE) 2 o
Stank effeet l shiftinq Splitting
Known as
lines of atons and m&lecules due to he
Speeral
Presence ot an exteanal eleehic fHeld J

Rotational AcHve l3nacive

H,0,sP%
H2 Hu, CHy)
CH,Cu,CH,
CHCl3
CH2
 Hicro wave (Rotakional Speckoscopy| RAMAN
Problems
Q wh heavy molecules have clnsely spased rotatlonal
end Level?
A
Ihe dislance between any two
0
ines is Constant end is Cq
eual to 28 (uhete Bis Totahional Conatant)
aBCT+1) 128- 3

Vi>jt 6B 2

0- 2 26-
O
VI2 HB
23 6B
28

For B h
C-H 8 B- h
c-D 8x
m, m2
+m2 spaing = 28
L Ond

f andspaing 28 V
B
why u'orowave Speeho sco py Could be done
in 9aseous state on
free 4otaHon 'shot possible in
A Solid i q u d meleules due to
AlgidL
n o t Possible intoy mole ulhu tosces.
Rotation about eaoh unigue axis
i s Solid
ic aucociaBea wNh a set of enengy level.
quanhsed Cdiscrcte
Chaving speeitic )iGtas
 wha is he qulrement of a mole Cle
to be mcrowave auttve

A Fetmanent dipole mo meat must

be hexe GLaseo us

for HU,CN, CO moleule

Deine Seleehon ule 9 hat he

is h e
SelechHon ule for Nicroware RotatHona!
Speobro coP
A Seleetion l e coRbrainhe Possible tranultionu
one state to
ot a Systcmn tsom q,uantum
Ohey.
absaupion
tor mcrowave it
AJ =t |
missIOn

0,1 2,3
o J S-2

S 3
which of +he following moleeule can havve
a Pwte totaHonal Specum

NO
ii)
CHCH
CH X
H20
OCS CHaT-
CO
N2 SF
CS2
 Numeuucal

Rotationa A
A
B
A
intunuelean
distance
B h moment ot ineha
8Ic Speed of Jigh
Rotational Coutan
2 I:.1151

F 28 6B 128l20Bl 3oB H28 68

8JTtD
Cm AT
= 2B
V3 68
2 - 4B
- 8B
V3- E2BCT+)
& Cal culate he hequenuy othe J-3+2
In PwHe otational specum of C l6 0.The
eui librium bond lengh is 12 1 pm

A a 8 6B
O12 xO16
m 2 3
6023xo23
6023XIo
m+m2
O12 + O16
6 023Xlo23 6023xIo3

ol2 X o16
Co12 t.ol6 ) x 6.023Xlo23
1 385 Xlo46 kg
 -12
U = 128 pm = 28I X1om
ly2

= 1385 x1o-26 x(112-81 x 1 2 )

2 T kgm s
45 Klo
-34
6 626 XloTS
h 8 x(314)*x3xio xYSAIO
46
8cT
Cvnls) (kgm*)
2
:931 Xo m
:931 Cm
6B
6x3
6 B I 586 m
The spacing betweenhe lines i n h e micro -

wave Specumn +HBr is 6.94 Cm. Calcuatc

he bond length othe mole.cule (H=I Br 80
2B 16:94 cm
B 6 .94 8.41 cm On
2
847 X1om
Ool X 08o
Coolt 08o )x 6 a3x lo
59 X1O' k
h
8xc B
-44
=
6 626 xI0 = 0033 X10
m
8x314)2 x 3x1o® x 2:47 x1o
12
I=uA l =
= 414 Xi0

HI Pm