(a) The fundamental an~-first overtone of hydrogen chloride are centred at 2886 cm- 1 and

5668 cm- 1·respectiv~ly. Evaluate the equHibrium vibrational_frequency, the anhamlonici_ty

constant and the zero point energy.
P.T.0.
 ( 4 ) 1629
(b) A substance shows a vibration Raman line at 456.8 nm when the incident radiation is
at 433.2 nm. Calculate the; wavelength for the Stokes' and Anti-Stokes' line for this
substance wQen the incident radiation is at 403.6 nm.
 ""
\
\
S.E C.J'ION ... B
6. Derive the foJJowing :
.I
(a) vma, ; 2.t = J
where .r,~f:s d~ anNiooo,nlchy constant of a
molceul,:,, Act ~ deli \~,e [Link] .:[Link] for the
speccnl~opic d~ialion energy.
1264
4
 . ··-
b . ~E . . == - · [!mg . .
() (cm- 1) · . ~\}.~ ·<-,::··..
. .
e
. where 6- is the ·[Link]~n .·between
'. . . .
{the maxima
.
in ·.P:.and :··R . branches··of .·a- . : ' , .
·Vibrational~~otationai .. [Link] , of a .polar
di~t~mic . molecule.
• • I • • • •

AU_.symbols have their

u~ual meaning~·
. ·- .
(c) Calc_ulate the ··popu}ation ~f J 10 ·relative to .
. . . . ·. . -.· .
the .'ground state. of a molecule if B, the ,
~
--·
~
~
-
.

,. ... . . . .
··rot~tional constant
.
is 0.2 ·cm~
- . .. ' .
1 at300
.
K.. 2,.2,'2
_7. · , (aJ .VJh11.t .is .Larnlor-precession
. . ..
. ?. the
.
Denve
expres·
.
sion· for .the Larin9r · precessional '
.. \
.
. frequency of a spinning
. ·nucleus.
. · .
8_ (a) State and expl~n the rule of lllUtuaI··
·exclusion. , ·
(b) A molecule XY2 has the following IR and
. .
·vibrational Ratnari-spectraFdata :· ·.·
.,
r (cni~I) IR ·. Raman
.•
, .~. 1243 . · :. Inactive ·. .Active ..
·2920 . · ·Active (PR) ·. ·:Inactive
786 Active (PQR} . . ·, Inactive
·. .
Giving . prope:
. . .
r explanation,
.. . .
.arrive
. '.
at : the-
. '
.-

geo_metry of the molecule. AsSign the Wave ·

• • I ' • • ' • •
· numbers
.
, . to s})ecific vibrations. <
.
9. Write short .notes ori:
(a-) Fluorescence
(b) .. Predissociation
(c) Factors controlling· ·~wid~s of· spectral
2,2,2
transitions.
'
{c' ) Htlw llltlfti)" tllfidc.,, u.f vrlbtation are possible
t""t\l' .C. ~>> ' j,. KCHOandC
Ne ·,. : · . . . · •. .A.. , : 1 H,6 !
 PART-B
6. (a) What would be the spacing of the lines in
the Ran1an rotational spectrum of H 2 ~ if its
bond .[Link] i.s 0 .07'5 7 nm ?
(b) Explain. ·the phenomenon of Fer111i
resor1anoe, with an [Link] .
(c) 1l1c :'1u11da.n,en:1al and the first overtone
ll3r ue centred at. 2560 and
111111sj1jo1,~ o f~ ·t~
~02.8 em-• ~.lively. Calculate the
a11l1im-.10,[Link]}~ etinstant and the force
1
cons:ran'l of HBr~ 6
1744 3 P.T.O.
6. . (a) Wfl,at is the ·trule (>f r1Mutual<e&c'lusion' .? t 'I ,
1
(b) A' moleeule ·AB '- has the foHowi_n • .j.n fra-red and Raman
2
lines :
C,m - 1 · Infra-red !
·-. ~---· · -R·am,an
• • • ... - \ -=-..... .
.l f• ~-:---v-- "\.
·3756 Very'· strdng; pe.r:pendi cular
3652 Strong; parallel
r
Stt&iil polarized
1595 Very [Link]; parallef
------------·---------------------
The rotational fine structure ·" o~f i'nfra:. red ··bands
is complex and does not · show sirnpJe PR or
PQR characteristics-~ [Link], n1olecular structure
' ' ', • ' j ••• ii' . ' ,, ' J '
and assign the observed lines to specific molecular
vibrations. 4
6. Write sl1ort note on (any three) :
(i) Predissociation spectra
(ii) Factors that control intensity of spectral
li11es/band
(iii) Fluorescence and phosphorescence
 7. (a) What is the essential criterion for Raman activity ?
(b) A molecule XYZ has the following IR and
vibrational Raman spectra :
V (cm-•) IR Raman
397 active (_l_) Vs inactive
658
'
Inactive active (Pol)
1533 '
ac tive (lle1) VS inactive
580,0
5 [P.T.O.
 .......,. -
Giving proper explanation arrive at the geometry
' '
-of the molecule. Assign the wave numbers to
specific vibrations. ·
8. (a) . re" and re' are inter nuclear distances of adiatomic
molecule in ground state and excited state
respectively.
three cases arise,
re ' = re" ' re ' > re" ' re ' >> re " .
Discuss the intensity distribution in absorption
spectra of any two cases, using FrandC-Condon
principle along with potential energy diagrams.
__ _ L.:""n lh ,
 ,l -1 l. "-' ,,,I
7. -(q): ;~#~[Link] #le· n.·m.r! spectFum.. of :~ thawl-:-un~kr:(U_Jow
. _· . -.:vtesoJution .and (ii). high r.e ~olutton.· -Clea:r,ly in-d,},:ca,te
. . ·. i:ilje relative position of the ~eak~ w!th se.spe_c t to ·the
., .• r~s pea,k. . Also give the rati9 of. the . p_e ak areas in
. . an~ th" relative intensitie:1{ of the spliJ [Link]:.s ·in
(i)
". _.,.,: .. '"'.:,. :>:(iiJ. ..(NegJ«;ct the [Link] ,effec.t.s of the proton
·
0
· . i, belongi'ng to .o.xyge11 atom.) · i· · , · · ~ •: ,. ; p h - · , ·
(b) Cµive reasons i11 favour of -the use .of TMS as· a ·refer-
[Link] [Link] in o. m. r. studies~
i
II
(c)· fhe chemieai shifts for the protomrin CH 3 F and CH 3 I
are resp~~[Link] 4.·26 an.d 2 · 16 in ·the [Link] scale·.
A.(;cou~·t . f~'.r ·~his i11 a quaijtative .\ll'anner~
, " ' • I>

4,2 , 2
 Section - B

(a) Why does H2 no_t show a microwave spectrum

whereas HCl does ? Explain with appropriate

diagrams.

(b) Derive the expression : Jm == ~-½

What do Jm and B .r epresent ? What are their
units ? All symbols have their usual ineaning.

(c) The fundamental vibrational frequency of CO 1s

2170.2 ·cm- 1 • Calculate the force constant of the
molecule.

(d) Why do intensities of hot bands of diatomic

molecules increase with rise in temperature ?
l½, 2, 1½,1

7. (a) What is the essential [Link] for Raman activity ?

(b) A molecule XYZ has the following IR and

vibrational Raman spectra :
y (cm-1) IR Raman
397 active (i) Vs inactive
658 Inactive active (Pol)
1533 active (11 el) VS inactive

:: O f\f\ fP 'T' n
 .,,..
( 5 )
1.~
(/) What do you understand by Larmour precession' ?
• • • I
How does the precession frequency vary with the
applied field strength ?
//
(g)/ What do you understand by pulse NMR ? What
\..,
is its -advantage. over continuous wave NMR ?
 (i) · What is prediss~iation ? Under what conditions
it is observed ?
6. · (a) · The values of Wose and Wose Xe for NO molecule
are found to be 1904 cm- 1 and 14.187 cm- 1 ·
respectively. Calculate the dissociation ener·gy of
NO· molecule. 3
(b) State and explain Frank-Condon principle. 2
7. '41,) What do you understand by spin-spin coupling in
~i NMR ? Sketch the NMR spectrum of etha.n ol
showing the splitting and intensity pattern. 2