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(K.L. Kapoor) Physical Chemistry VOL. 4 (B-Ok - Xyz)
(K.L. Kapoor) Physical Chemistry VOL. 4 (B-Ok - Xyz)
size wis aay eran 2.
Making wse of the expression ApAx> hi, show that for a re particle
‘
seat
whece BE and Aare the minimum unseraintes in enemy and duration of measurement
of velocity, respesively.
For fe particle the energy expression is
pe bmte E
aon
‘The uncertainty in energy will be given by
sE~25p
Wave Mechanics, Energy Quantization and Atomic Structure SI
sere Bp i the wernt in p- NOW plo, which is veloc, may be measured by
Recang he ditnon Au eaves inte A, sch that
zat
nh
tras the maximum uncerainy in postion ofthe parle drng se measurement of
then the sium uncertainty in the value ofp wil be
2(2)4
oe(R)a
o2 ipa St ap2(A)L
vee 6 = 2 bp SE Bp2 (A) E
"h
«eat
‘one-dimensional box wit the origin athe cents
‘apr of mass
‘he to + 1/2, The potential energy is
ofthe box. The box ex
(0
ne, mar
Co te ebsing gain the sytem showing separate equation fr th
‘and the outside ofthe box.
Sind out it c
{) Derive the enegy expression ofthe particle.
(4) The Sehringer equations are
(@) Inde te box
Bey i
- =e
aon a
in the expression
Gn) = A sin(aa) + Bos (ax)
we get
‘Asin (a2) + B cos (al) = 0
and ~ Asin (all) + B cos
‘Oa adding and subtracting the above two equations, we Bet
A sin (ad) = 0
Bos (a2) =0(er
cn
aeep
ord
bo seo 293s
fs 99 peta
senso mato > 0982
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a a ons oats sage 99H
1 (p22 (28) [x22]
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A (22a lzxe[xe2]za
see) oor
y ze @ | ye o
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om Zax Gig +ZAN A
ns
sonoury 20nn a Gz poe CK CK a
wyo aiztouene = 2°94
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= mt
as
# 77
ssono sonato taponas an 32 = (2)(22) 7 aay
Pp Ue) bp)
UIs xm] =x ER =¥ wO= x MY OSB Hx =X PT
‘womenioysen
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omen
ve
128 om omens
Exp Bunransqns Wo (2)
‘ectew
assep om no Sark ps
wwe (2h) mya
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{uo toga wans) 19 y 2-= w qu YP = ug = Boy
(eo) us ya
9 vans 2g wonouny anew 999 = @ 205
“uo zaqumu ppo) 6g = w a= x = ak
(em) 9009 =A
4 want oq ny wonouny anew a9 = Y 30
5 Ue U1 A = 2m 20 0.= a ag a4 na 3p) “be
°C 'T = 4 Mu = 220 209 = y so oye nts 3m“) a0
soy pu
asc reomtya fo your, ¥ 7S4 A Textbook of Physical Chemistry
E=E+5,+E, 2)
we have three separate equations tobe solved, each of them has & form of
one-dimensional box. Thus, the normalized wave function ofa thee-dimensional
box is
J
(1428)
‘The constants @,, @, and a, will be given by
(1429)
and thus the total energy is
x
Ba E+ B+ b= | (1430)
‘There are three quantum numbers, one each for every degre of freedom.
S$
Example 1.43 The ground state transatonal energy of a particle in a one dimen
length is about 4. Suppose thatthe sare particle is moving in
Pog, + (Pocy.~ ex, ~ Pex, )608'70.52")
147D + (147 D~040 D ~ 040 D) (0333)
-147D+022D
= 1394038 D=176D
Pe (Peay ~ Pe) 81082 sin oP
=o
‘The dipole moment of CH,Cl, will be
pe pi toi + pi = y(-125Dy + 76D +0
=216D
Fig. 3118 Orientation
oC CHCl, molecule
We have
Pe®Pou* (Foo, + Pox, Pog.) es (7052")
=040 + G x 147 D) (0333)
=187D
05)
Let the bond moments be resolved into the Catesion y+ and
18
Poe, + Pea.) sin (70:52°) cos 60"
Electrical and Magnetic Properties of Molecules 367
ating the dipole moment of benzene derivatives, the study of group moment
than the concept of bond moment. For example, in
‘moments, then the observed dipole moment of 1.55 D of ehlorobenzere may be
anise fom the CCl Knkage, Thus the group moment of elorne atom
the group moment acts away from the
benzene ring whereas negative sign implies tha it acs towards the ing. Table 3.12.1
Includes the group moments of a few groups
Table.
Group Moments of a Few Groups
Group NO, CN OH Gl oH GH, NH
(Group momen
Deiye <398 38 16-158 0 404 4153
‘The dipole moment of any substituted benzene can be desived from the following
‘expression of Vector addition of group moments. Consider, for exampl.
arrangement of two bond moments, and p; inclined at an angle with res
‘each ole. Te aditon ofthese two may be cared out by ang separately the
two 2 and y-components of py and py 50 ato give p, and py respectively and
then by employing the expression
P=@i+ 9)!
wwe get the resultant moment ofthe wo moments If 6 and 4, are the respective
angles ofp, and p, with axis, we bave
PLE Phat Pas PLS A + By 08 0
y+ Pas isin + P30
cos 6 + 008 8) + (py sin +
ene, the angle @ between the two vector is 6. Subsiaing
+ 2p,p,<05 6)!”
pau = 4 #4 pp cos OO2 = Sip 1oes
sn (@609~ ovr + So
EL 509 (GST -)E6E “IC LCST) # LEED = a
auaruagosoioye'T
wl
aeee-='ond pu agst~= "9d
smuazioqeamosoye-y 1 pie ECA)
coomorion-d
0 + c1Z0 +20
ql 021 50 (0¥0) (851-2 + {00+ (SSI) = ad :ruoMomVORD-
61e'1 = (1060 =
L0~T1C0+ 20") =
1+ fOr0)+ 651) = aM -suomormoR-o
‘vat
aovo= 84 pm asst-=4 aH
smuomorosonyd 4 ()
axl09 99 (OF) Gs
aecy=aovo+acee= WM +
sono2s
tutod ean ot 29 se suxwou 2pdip om a J BOMIPPE Fee
Sydans 4 oan pence aq eur wou =odep xp 2eanfoantd 30 ourowsoy
Gey = y(919E + ICO + SoYSD =
salts 509 (976) (6° “Ie + 19P0)+ coe) = a?
sm ost s1@ aay uemoruned
ary
S97 LD = a 9081+ 210 + SH¥SD =
ql0E1 99 (0¥0) (€6€-X+ {970) + 66¢) = aid
sm, eI S@ Bey momo
WE (B08 T1Z0 + SH¥SD =
0) (66 e+ Y9r
eal 909 Uldr 4 2d 61d) = ud
out 09 5 9 aAuY sMoMOWNNKD
asvo= 4 pwr qese-='U
ara,
“0 (a)
ond
asst=4
aszeaserezei=d
ond: ouecuqupoup-d
ovo= 4: svamqiousp-au
ausr0=a9v0x cewi=d
sourusgyqioutp-d
o=d = ouaruagonnup-d
eee=d + suemmqonp-a
aivo=aserxcect=d + avamqonupo
souaruogasuped “140 (Q)
ney om ‘09g
a="
agp 24
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“eon en hq pertpou 9 Au sw=won poog yo spre a4,
Sones ap Jo wo
3 Ig HOM ABLE =,
yp 0 209 29 Seu
s] eau yp sone osama a op Em)
dott
rez = aoui x cet = te
any 2 Jo asa at Bu
“Ayaaaodsau “q gor ?
sea ctmy aman ees
Spend oo
eve oduexg
an me a= A ye 0 dl +
whan
Casmuoyg yorstya fo yoou2y ¥_ g9e310 A Textbook of Physical Chemistry
3.13 APPLICATIONS OF DIPOLE MOMENTS
Shapes of
Molecules
Geometrical
Isomers
pSubstituted
Benzene
Molecules
Electrical and Magnetic Properties of Molecules 371
LA-chlorontrobencene
‘The two vectors point inthe opposite dzetions, and hence the magnitude of digo
moment is
(@ydroquinone) has a dipole moment of 1.64 D. It leads to the conclusion that
(C—C1 bonds are coplanar whereas C—OH bonds might not be so
MAGNETIC FIELD IN A SUBSTANCE
In vacuum the magnede fx density Bis related to the magnetic Geld intensity
by the elation
p=393D~155D=238D
B= toll AL3Ib of Annexure
le moment values i in the field of molecu ee heer ne _ fa
ene of symmetry ls dipole momes thin a substance Bis, in genera, not given by the above relation, It may
roups ae symmez _reater or less than gH and is given by
r dipole moment, A few exampl B= (H+ if) ere)
the structural application of dipole moment values are now describe.
where isthe magnetic moment pr unit volume and is known asthe magnetization.
The dipote measu
molecules, For exa
have zero dipol
zero dipole moments. Ths, it may be concluded that 4
molecules with centre of symmetry, and the later are nonlinear molecules. Hence,
the structures are °
jn magnetic feld. In SI
‘The magnetization of a substance is directly proportional to the applied field
and is ths given by
Me xy (Blig
where 7 isthe dimensionless quantity known as the magnetic sus
Te lowing yp of saan ae finer pening oon
magne
ee Fi
the onder of +108, The magne
thus B> H.
Diamagnetic substance For sucha substance,
the order of 10%. The magnetization of th
Bed,
negative and has a value of
tance is negative and thus
planar, Some of AX; (PF;
have zero moments.
structures are
Experimentally, the more useful quantity i the product of magnetic susceptibility
' and mol hme dened os
. = (Mar volume) (magnetic suseptiiy)
nee Recdebok - (hx 6.
Ne Neo « Pp 5
i % Sie has wo wit th oni of is that of oar ole, ma
: i 15 MOLECULAR INTERPRETATION OF DIAMAGNETISM AND PARAMAGNETISM
x Tag oso Ine previous scion, We have defied pe of magnetic mts based on
the sign of intensity of magnetization.
ianagnetism and pat
this section, we describe the molecular
agnetim,
se t distinguish between the cis- and trans-forms of a molecule from
iamagnetism The diamagnetism in atoms, fons or molecules is due to the orbital motion of
pretation of diamagne
Dipole moment values have been used to show whether the linkages CX j
in p-substituted benzenes are coplanar with the benzene ring oF not. I.4
dichlorobenzene has 2er0 dipole moment whereas 1,4-dihydroxybenzene80 0d 99
61 0g N=N
ue io Neo)
ss P09 =9
a
Db
08 uy SU0N 35
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£Le myno2}op fo smuadong auauBopy reo UDA asta jonsiya fo yoo ¥ LE314 A Textbook of Physical Chemistry
Electrical and Magnetic Properties of Molecules 375
The paramagnetic susoe
suscepiibility can be worked out and is fou
‘Table 3.17.1 shows the re
of unpaired electrons.
1 be expected for 7, at 298 K for various number
ar
Table 3.171 The
lues of Molar Magnetic Susceptibility a 296 K
the only ctr which opposes the perfect alignment of dipoles isthe thermal ney Number of Taal electron Spin magnetic
Larger the thermal enecny (i. lager temperature, lesser the alignment snpaind spin quan
lecrons __rumber S
3.16 TOTAL MOLAR MAGNETIC SUSCEPTIBILITY Oi
etal le moe cept ith agra sum of maar ana 2 2 ans air?
seen ad cer rng se sum of E9s B.15.1) ant - 5 se joo ei?
a ‘ an 4399 12661 x10
fa Wy{ + 22)
fe Nal ig + 5 sn 516 16453107
For diamagnetic substances, i, =0 and hence 6 2 578 252.90 x10"
Tn = Nn 43,
ii’ GOUY BALANCE METHOD TO MEASURE MAGNETIC SUSCEPTIBILITY
Thus, diamageetic susceptibility
{In the Gouy balance method, the sample whose magnetic suscepaility is required,
independent of temperature,
For paramagnetic substances, both the c
substance, zq 8 usually of the order of|
diamagnetic contribution (10 per gram)
butions are present, For such a
10 per gram and thus the small
werwhelmed. Thus, we may write
(3.158)
n slom, molecule or ioncan be worked out
15.6) and (3.15.8). Thus, we have
Pie MBA Exper.
tena set upof the
balance method
[i 10
= 4x (1.68 » 10° mm? mol eur.
‘The molar megnetic susceptibilly 7, can be determined experimentally
Knowing Z the Value of $ can be obtained from Eq, (3.17.1). The value of S
‘us obtained can be interpreted in terms ofthe numberof unpaired electrons by
using Eq. @.15.).
snd minimam
experienced by the sample by consieri
segment ofthe sample and then inte(arnt
papi
aay
‘94, 2oumen Satandsoss wut poowd sem pena
4,01 x I=
(aa ,s000 PI
susnos)
oH) ay ( 8) 2
(3) le) 7 = m7 sm
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SWS E = wey
oo o0R6=#
ON 01 tp= 0
sm 01 =10W Vigan T= A
Jorg 01 a00aY =
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apow aq avo puw Aynignidacsns anauSew 2qp or porters} 2axoy stu =
asquoyy roorsiyd Jo yoo9nay ¥ OLE8A Textbook of Physical Chemistry
‘hich on sustitting tho data gives
200.4710“ NYG
dgx10m (0A
Ya
$2156 «104
REVISIONARY PROBLEMS.
fine the fllowing tems:
‘molecule in the presence of an electostate field.
Aistoron and orientation polarizabilities.
(Hin: See Annexure I atthe end of the chaper)
3.2 Desice the following:
3 (or stat coulomb) = 1 dyn! cm = 1 g!? em st
lenias
D=ol
1C = 2.9979 x 10? sat C
“The unit of woe ig erg (esu)* or JC
1 erg en ear= 1a V) ent
SIN TEV SY a"
The unit of dipole moment is eu em o¢ © m
1D = 3338 x10" m
‘The unit of polarizability is em? or C? m NE
The unit of a4 is m*
(Hine: See Annexure 1a the end of hs chagier)
33 Derive the Clausiue-Mosot equation:
led ML 1, gy,
(ele)? p ~ 3 0%
Explain, why the above equation is applicable for nonpolar molecules and not
for polar molecules
34 (a) Debye equation is
ain, the nature of plots of Py versus UT for i)
nonpolar molecules.
Electrical and Magnetic Properties of Molecules 379
(8) Debye equation canbe ued to determine the dipole moment for molecules
in gaseous system, whereas it cannot be used 8 sich for molecules in condensed
system. Explain,
(6) To determine dipole moment of molecules in condensed syste
preferable to plot Py I, where Piste molar polarization of
ite dilaton.
}) The molar polarization of a
ynereas that of a nonpolar molecules is independent of te
why itis so
3.5 Explin, how the molar polarization vases with the frequency of an electrostatic
‘eld.
3.6 Under what contions, des the Matwel relation D =r? hold good? Explain
why for polar maleuls D =n
37 What is molar reaction? Show that is given by
y= Hoh M2 Mag,
Fa2 pe
38 Desive the relation
pC m= 4273 x 10 (Pg ~ Re? mot} (17!
39 Explain, how te dipole momento a azomic molecule determines il er cent
ionic chaser
3.10. What do you understand by the tems bond moments and group monet? How
oes the dipole moment of diatomic molecule or bond mores determine is
percent ionic character?
AL Show that the vector ation of wo moment pan ps ince at an angle 0
is given by the relation
pie ph+ ph Dep, cos 0
312 The dipole momeat of he faving molecules it 2ro, Wha do you coche
about thir geome?
05, C5, HgCl, CH, SF NCO),
sie fee on & moving charged pace is known asthe Lorente
ven by
008
of magnetic induction 8 is given by
basic
=10'G
(©) Show that cersted = LA minx 10°
(Cine: See Avoexae I
4.14 (a) The magetc eld aa distance d produced by alec cunent/Nowing
inalog sight wie is
(9)
‘Show that Hy the permeability of vacuum, has the nit of NCSp amantzors aout Jo aye an up 3 1460 8S. PE
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Supp 30 pod you 21 uonquaun agemoseyan we sy ue paressu08 am)
‘yin uy onze Jo Sons Jo os se paoUse He PORN Au Jo rots
onoanp am 6 9 suoneues oy, poy anouBeu uaa oF oNOUBEW UR
seranu ain oetanap dejo ray sey Spey smear mn jo Glove kBJOU ONUaIOd
SAL Ey Big anos am pjy apeuFeu qe M4 pueda jo suonENeA au Jo uoneuen
Ewen wi-stw tg 8 e)-=
wen w="
om 9 s00(14 9p 8-) g—=4
188 an (©E) ‘ba oy jo uopsaxteo an Sunransgng
(sew) (9 900 "“t)q-="a-=A
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ond stg pray onauew x ur paoeyd ways uos2oj9 we Jo A ABI0UD emUeIO’ ea
Preig onauBeyy
oufeutjouoneua}20
aL Tey ha
BUey fy ui umoys se umpuowous syndue 249 JO 7eH) 07 280%
StauBeu an Jo wonoasp a i seat (ee) bg484A Teubook of Physical Chemistry
Fig.434 ESR signal
and its derivative
Hyperfine
Structures
Molecular Spectroscopy 435
the signals are ecnde sth derivative of the abortion cave wih eet
the magnetic field, The typeof derivative which one gets is sown ia hg at
Nem B-(Ue
y
‘The interaction of the magnetic moment of an electron with those of
depends on the lave decon ofthe negnee moment he clesion lee,
‘otha ofthe proton. This interaction eng) exese! ss amgm hae ene
now sthe hyperfine conning eosont othe pene png
fepreseats the exten of interaction between the slecfon sad he 4
imercig nutes
The separation between these two absoepions isa. Thus, th constant a represents
‘The electronic energy including the above iteration energy becomes
V= giigm.B+ am,
Thus, for a given value m, the potential energy also depends on the valve of
my, Fora proton, we h
andy SE em moi
bv
Bin my HD
Bhhy Zale
: iy ya -
Yanan =~ U2) EHy8 and Beem m1
Ble Tele
Where the fist subscript represents the value of m, and the second tat of mp. The
variations ofthese potential energies withthe external magnetic field are shown in
Fig. 4.35, The broken lines represent energies i the absence of interactions. The
value of B at which adsorptions are expected (only schetiatic) are shown atthe
ofthe figure.
For example, the ESR spectrum ofthe hydrogen atom produced by electc discharge
is shows two ESR frstderivative signals with eparatio
‘The energy of an unpaired electron coupled with two nuctei is given by
Y= guigm,B + amy * cam)pew ON
ypuosouo ay se asuanut Se 2 2 fs 9UH BOP,
See | Sid
possnosip
a=
1 wonoesany 3t9 01 sp paasosgo xe
Safonm agp ys UoHDesUN 9g UO 20
‘pansosqo 9q {1M S90!
soseoqns oait\i4
ui-= Hw
wits 4
. (ey Fup Aeanoedsa
Fe ; a pu Nw 30
Pay PLE puodosoxp pu “uo anjea amp swaeanda Eo
ng am aI0H 4
wins tw 4
tu ie
wits the eB - = Ur UE eg
= aura,
‘gp 1 pantasqo 29 11s ‘|
uits tw 2 UU,
= euros
w-= tw
anes y= ats ty + at (qs Hoy
an-= th )- ate remem,
2 Ps pausgo 2 ory
nos 30 sofhious m9 (g/=uy pur = wv) se] won 2m) FOEKOTL a
A
Adoosousods sno}
or ae Aanpuaye porsyg fo 00921 Se438 A Textbook of Physical Chemistry
Interaction with The ene expression wt be given by
Nueet Ve gilgmB + ony, + mm ++
td the resonance condition is given by
Wye £162 + img * amy +" * Oy aay)
The sumber of mys given by te reaton 21+ L,where Ps he spn gut
numberof the sults. This, the interaction of et lec Wilk nea ives
eo sons, wee
N= @h+Qh¥) ~@h,+ 310)
‘A gece of meres ith mentioning her. Tiss when all te n prs
aida i. ay "== ay The fesoanee conti
Molecular Spberoscopy 439
BV Big B amy + my + + my) aay
If vis held constant, the values of B
by the expression
Bm Byw a! (my + mya to + my)
Since fora proton the permitted values of m, are + 1/2 and ~ 12, the sum in the
above parenthesis can have (n+ 1) different values as given by
prem eee (eel
Barbe GE-5
‘Thus the expected numberof lines are (r+
ach oer. Te intensity ofan absoptio ly proportional tothe
degree of degeneracy of the involved levels. The relative intensities may be
computed from
hich absorptions are expected ae given
ile ml
1 The above scheme my be ilustrated withthe example of p-
'*
‘The benzene anion radical may be prepared by the chemical reduction of benzene
‘with alkali meta in an inert solvent such as 1, 2-dimethoxyethane or tetraydofiran.
6: 15:20: 15:6: I with a hyperfine spl
semolecular orbital which has @ node inthe plane ofthe mole
carbon atoms have zero-lecron densities. However, this n-electron
clectron pairs of C—H bond, eausing hydrogen atom to have a some unpaired spin
density which accounts for the small value of hyperfine spliting constant. A useful
relation between hyperfine spliting constant (a) and the unpaired spn density (p) on
‘he carbon stom t0 which the proton is attached is due to McConnell
84 Oa
where Q is called the spn-polarieation parameter. For x radical
1
For methyl radial, the value of gc will be equal fo one, Hence, the hyperfine
spliting constant of methyl proton is expected to be 0.002 5 T.
polarizefaveq pur gs Seo 29 I ur CaamIeq woneRedas ayy “suoosd wopetnbe ow JO
faosaed op cv anp sou 2p OWL eS Aga ee 20 YALL "| Jo uoneneds aN
‘ sonesusiy nba jo (@= 1 +72) sou 30u cn yn Tvs 20H YS ON, 200,
1m $¢0= 2 7/1 =1) sro waqeanba ow por (im cot
52 [= 1) snopon Ny, 0 Sou. sped Jo urd sa Yo uBO} 2 OPA
9
Anon 292s ang or ao om Sau Zp U0 oe SAE Ua
pee hu soquinu mmuenb Yow La OZ = *P PLE LW OT
(erta
sou aumsady om op soy weya ay “Lu é ze wo panu2o wnmaads san uz
‘ur u 9'Z soEKUaD ZumAds YoU sucosd wapatniaaoU on) BumURaNOD Tepe ¥
a3
eee,
Lceeo= i
axe amg = Ay 9UI8 WON
x se99)=44 = AV
1 «Ol * 2086 = mHD OES =A
Fy. 0t x 1919 =
tan 2046 8 Fondo wowanoods ©
‘ok pnom eM EY IY °S ZOO Jo anTes-F vey 2H°D UH
panei, OL €1 PEEL ,01 x HFA SEE poAOHD
“Ly.O1 x ELT = (216500 (LOL SD= "0D =» samy
zr6800 5
omy ,629710 20 JP 9 5" sUOGID Jo oR Wo KsUaP UNS VORDATP- mL,
Lol coy
(60810) 1 01% 50) 909 =o
‘so03q 60870
‘nym S780 90 PUR gp *T suORRD Jo yea UO AasUaPwHES woNDefo_K BL,
OM @ = Mo ‘wonearouwe2yy Bsn
a pamuupse 29 we suord yo spur oma ssay 30 sas Samandsauyzedy ou,
suojnd Jo pur poo
‘gy asa Jo ue pu
todo an “soup suovoxd 390 SuIUDD Woe ‘SvORNM
1) aap Svondsge ang
apy om Se auaTeNYCEN,
Teh Sdostomeds s9no2y0y4
vonnies
very ordusexy
4 t
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eons
day
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-30 3 cot onan oped 27 toad nok Op
sorase 4S
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arent tut 11
seututdurambrty
buunatednitii
austt
‘swore uoqies fp » 0 anp simasuos Zunayde ously yo Sones a pala
’
CO
wh
8 soo8 avopngdeu ur soe uogio Jo Buaquana aay
estro= i
0 seRoefou pavnoooun ea
H uondosge ys Kuew oH Pep ordwexg
owe oypes
suounbyassomn
jounspods
asd eer 2a
Aasqucyy poqstyg fo yooaran ¥ Orr442A Jesbook of Physical Chemistry
Example 4.3.5
Solution
Fig. 439
Example 43.6
‘Solution
Molecular Spectroscopy 483
5 ach of the
nes
= By + (0224 mi) + (0.268 maT) (42) = By + (0.626 mT)
Byy= By + (0224 mT) + (0.268 mT) (1/2) = By + (0.358 wT)
= By + (0224 miT) + (0.268 mT) (~ V2) = By + (0.09 mT)
= Bo + (0224 mi) + (0268 mT) (~ 312) = By - (0.178 wT)
1 respect
By = By + (0268 iT (12) = By + 0.134 WT)
Byy = By + (0268 miT) (- V2) = By ~ 0.13 riT)
By = By + 0268 0) (32) = By ~ (0402 iT)
The relative inesites ofthese Lies wil be 2: 6:6 2 respectively
yy = By ~ (0224 mi) + (0.268 mi) (372) = By + (0.178 mT)
y= By ~ (0224 m1) + (0.268 mT) (U2) = By ~ (009 mT)
yy = Bp ~ (0224 mi) + 0268 nT)
= B,~ (0.358 mT)
By, = By ~ (0224 mi) + (0.268 aT) (~ 372) = By ~ (0626 mT)
Predict the appearance ofthe ESR spectrum ofthe ethyl radical. Given: a
0.204 wi? and a(CH) = 0268 mt.
Fig. 4310
For idetical protons, the ESR lines are observed at
hv
ee ays tmnt ma + 4
By > :
For mete protons ay at he vis of, Od. Hent te tes
"lave imate 1:2: Till ebere
B= By +0204 wT
B= 8,
By = By 0.224 mitcg =4 3
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138
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asspuoyy yorsiye fo woaeL Vee46 A Textbook of Psical Chemistry
Carbon monoxide For CO, rey 113 pre. The reduced mass is
Hoy = Patt = (CBIR 6.023 x 17 )H(OO16 Hg 6003 x10”
Ince (ODI2Kg)/(6023 10)} + (0.016 kay (GARD x10
14 10 kg,
‘Thus, its moment of inertia is
1= P= (1.14 x 10g) (113 x 10 mi?
= 14.510 kgm?
A (66261039)
Bele” SG IFUAS x 10g m9 ED
1932 x 10? mt
‘The value of rotational constant in joule is
Bho (1,932 « 10% m") (6,626 x 10 55) (2.998 x 108 ms")
=3.838 x10 5
‘Hydrogen bromide For HB, rn,”
Hence B=
14 pm. Thus, we have
=e.
os £(0.001kg)/(6.023 x 19”) (0.079 9 Ke)/(6.023 x 1025
0.001 g)/(6.023 > 10} + ((0.0799 key(6023 x I
= 1.64% 10 ke
Jae = HP = (1.64 x 10 kg) (14 x 10
$3.26 10° ke m?
A
oe (6626x1074)
ane ~ GIAFG26x 10 ig m9 IO TY
© 8.595 « 108 ar!
‘The value of rotational constant
Joule is
Bhe = (8.595 x 10? my (6.626 x 10™ 5 5) (2.998 108 ms)
= 1707 105,
‘The various allowed rotational energy level for these two mol
in Fig, 442,
sxe shown
populations of energy levels can be computed by the Boltamenn
2 = exp(- ABIET) (448)
And ny are the number of molecules in the lower and upper level
and A Bis the energy difference baween the two levels. The pop
ineach level is given by the expression
ny exp- Ey/kT) (ag
Molecular Spectroscopy 447
se
sas
jews 0 res
sett ee
i ue some
see
i — Ana 2
4x04
5 is ary]
i
vot} ye
a
a eas
wath a a
it
——
=i
, $4 to
= vee
Since the molecule can rotatein 24 + | different planes withthe same rotational
‘energy, the various rotational energy states are degenerate by a factor of 2 + |
“This factor is known as the multiplicity of energy level and is written a8 gj. The
probebilty of occupancy of these degenerate states are completely identical and
thus all the degenerate states are equally populated, Incorporating this malipticity
factor in Eg. (4.4.9), we get
e006 8) a0
From Ba, (44.10), we may waite
Be QE DEMCEMD ID sap agury (an
ne OF #DespeE nl)" GD
where J’ and J”ate the rotational quantum numbers ofthe higher and lower energy
levels, respectively.‘aqnogons amy Jo won 0 Kuanbay mp3 no st ouow 2d YO
wouodio 2¢p Jo uonenony Jo Kovanbay au, "p yp 315 u wnoys se Kenypousd
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Ausyuo postya fo yooursa, v $Y450 A Textbook of Physical Chemistry Molecular Spectroscopy 451
' ' ;
Jo folot
ee !
meee Pott
“ anceot
(44.14)
els
When the frequency of fluctuation of the component of ‘ >
frequency of rotation of the molecule) becomes equal
component of the radiation (the fequency of raaton sel, there oa
han on absorption li. I fat,
in Table 4.42 are observed,
pore rotational spectrum would consist of mo
‘8 sezes of absorption lines atthe wave numbers
‘Table 44.2 Energies of Absorption Lines in @ Rotational Spectrum
those with no permanent dipole moment
ane knowa as microwave inactive molecules, »
‘The homonuclear molecules suchas Hf, Ny, O> Cly et, ave no peamaneat w
moment and heace do ot exhibit the roational spectta Molecales having @e
of symmetry do not possess permanent dipole moment and hence als fal
88
108
Solecticin Rule
that is, the change i the rotational quantum number
indsivng ie selection rile for rool ci
7 ‘The spacing between any two nearest absorption signals is
ese transitions are not equal
noted from a given level depends on its population,
‘molecules that can be promoted 10
the foot of Fig. 44.5. There occurs a progr
boginning and after passing through a maximum, it diminishessou,
um ycioe=°az pur wo perme = Ptgg
sp uaa axe 394
eo anode, you F Q9On-ZT UE, JUN
POP Ogy 3 S065
'¥ Zr 990 or pund} S| OD, 10 vorsbosgeTeuOHIO!
sommsuatut vondaosqe yo uostdieo ayn wos ovepunge axe OH osTe 19
10 ou sd} uorstunsqns a:donst
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jou ¥ UL HOT Ayaan red w UY,
$1 anaotou O39 3051 30 somyea a,
esp Adeosousads somom0H1
($3 01 x 866;
4 stop w=] MON
2, 01x SVT =
C01 x 9299)
saa
‘9 ‘sonen 219 3
gs
BS =) sopon AES = coms
18 OX ZITST= mC 1ST = sou
peg TEE = ae = 8 ooueysig
‘2A 9 ‘SmyL @01 Toba st SIE, OY ZH puog oujwuar9q,
‘aoods ouput 20 8 ap ojnaotous QO Jo 959 al ‘afGuERXS 3052, z]mosIoM oY uuNZads OWN
ee eye,
GF oyuowesp © o cours paog ap oursirep or posn 29 ue nares uoneos my, JouRaNdY
ee
i
T
ejay mayads aon
i ready srr
casuony porstye [0 Youre], ¥ 2p454 A Tenbook of Phys
Example 4.4.2
Solution
Chemistry
192124
‘Thus ee
18367en? * (12.0000)
Solving for
‘The momest of inet
nd the period of rotation
energy level has th highest
Population at 298 K? (e) What isthe change in solatonalconsast when Hs replaced
byD?
‘The diference between the two successive energy levels a given by Eq, (44
or B85 em"! 845 x 10 at
Now Bis piven by
(aT
where fo Bris
= 142 x 10" m= 142 pm
(6) The energy ofthe rotational level for J= 1 will be
B = 16.90 em! = 1690 10 mt
ex Serpe
23357 x 10-27
Molecular Spectroscopy 455
‘ron classical mechanics, the kinetic energy E, ofthe molecule i given by
Pera
3
where isthe angular velocity in radians per send,
Hence
ion of H by D does not affect the intemuclear distance of HBr but
changes only its reduced mass. Sine B is inversely related to I, we may wite
= 4278 emt
(2) Show thatthe frequency of rotation (=) of sgid rotator increases with increase
{in rotational quantum number J according tothe expression
Pre
ve pa VID
() The increas inthe frequency of rotation increases thee
‘fo move the atoms apart. Consequently, the bond length of dit
wit neease inthe value of Je behave srg rotator
8 nowrgié:ottr. Fora molecule executing simple harmonic motion and bebaving likeTF OR B=
Pig Oix iT MUR AA | oy
peNoneses] 1" A 1
HN OL see =
Gomeorxsoe)
WH BEORY OT pix Ear
a
pian”
on
swung oS
-o1xse1_)_ ah
wi epiamyorxewis (eet) th,
gmemgancaris (SEE) Hey om
go eo) 6 60
M1 ,, 01x Jee =
(8001 866) (MOT LY LITO
Chg 01 299)
128 a Fanon tn Bunnag
24,88 21,88
2H atom AEE a g sous me
EE tan PEE gc mon
it Or HOLE
19 EL =
sof amc pur g 3) Busos,
(oe 2 SSETOI
n> ssc TOL = Fal 998g
ilo prcygs Pearse
Ish Kdooromeds somomoyy
(+p =
DeT~ (1+ DEB) ~ (0+ 0 +N = (0+ (1+ Pa) =
ig -ig egg @
:
398 am ‘(z) pus (1) sb Supenbq
Agure= ase ©
eee eee ee
T
4 wand s poaous ap 30 ABsova anoury ap “ofan eye oF BUNpIO09y
Bem ap son ay ey mee om wang ae om oO
ons oj mn mos (ep Bog 2H) pod Jo rr> 2m) a O08
yee
pie
snduo tn Ag san 8 pu yuesue> WoRIONp ERRGENEDD Se UMOWY St IH
uonnios
_Aussmey wri foYoOmtaL YO458 4 Texbook of Physical Chemistry
Example 4.44
Solution
eat atom moe
'N and DCN,
rom the following fats sbout HCN molecule
u——c N
en Fe
Keene
by Se conto ity
‘we may write
Balancing the moments about the cenze of gravity, We get
; art Mer = Me
Expressing ry and ry in terms of re withthe help of Eqs (1) and (2), we get
alte 0) + mere Mylrea re)
ures — mare Mow — mae
Img eg me
where cs = + Met te
“The expression of moment of inertia is
°
Tnen = mri
Expressing rc and
mur + mardy +2 (mg + me+ my) + re gre — My Fx
= mardi t meray + FE mye + Rel em Fen)
ing ror Eq, (3), we gt
en = my a+ erg
(ests
2 BE) areu ~ muro
the requited expression of moment
ule, the coresponding expres
all, We calculate yey a Foc 0m
and Bp espetvely. The rotational consan in frequency
unis given by B= h/BxI, Hence, we have
Molecular Spectroscopy 459
hao BE
in! Trex
wt oe te
8x? Boon
Subscting the given data, we get
eee
F (asaiso7 ioe
= 1895 x 10% Fo = 1.895 10 kg
1
Gemma
= 2315 x 106 5 se 2315 x 106 kg on? a
107 kg mot 35
Now mys cl BBL 165107 6
GOOS% Part "NE IO °
2 2X10 KOI a9 0%
rig = ZEIGT, = 0382 10 tg
2x 107g!
© 6023
= Mou
ay
16% 10-™ kg) By + (2325 x 10° ig) ry
(656% 10° eg) Fe — (2.325 x 10" hp) roy?
(166 + 1993 2325) x10 ig
166 ray = 2325
a8
1895 x 10m? = 0.166 ry +2325 ry
of BSI m? OTIS ry + 502 ry +077 re Pow
et = Fey We have
a3)
by 2 and subacting from it Ba,
m= 463 1
624 x10
463
Now substituting yy value in Eg (13), we got
LAB ry (1.79 10” my ry 348 X 10°? a? = 0
Multiplying Ea,
624
16x10 m
Solving the quadratic expression, we get(yr = axotvw
Cy) = faxzytyt—
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Classicat Potential
Energy of
Harmonic
Vibration of @
Diatomic Molecule
‘Wtng the above equations inthe determinant form, we get
| mOn my
& m(2nv)? ~ ky
Jn order to have nontrivial oos of Ayan Ap, we must have
Wh
& ma QR) ~ by
Opening ths determinant, we gt
my, (2nv)* = ke, ORV)? — kem, Onvy? + kena kPa 0
or mymy (nvj?— bem, + m,) =0
ow ved [de
2m Yorum, jComym) 2 Ve
Where {= mmm, + m) and is known as the reduced mass ofthe molecule,
Equation (4.5.10)
Aistomic molecule u
=0
45.10)
he required cf
rge harmonic
istic frequency at which atoms of
‘The potential energy of a system at any instant canbe evaluated from the expression
san
Tn the present case, we have
av
whee Ta
oe Wak Arden)
On integrating, we
Vek
+t
2
‘where 1 isthe constant of integration whose value may be determined from the
fact that at Ax=0, V= 0. Thus /=0 and the poteril enecgy expression becomes
Vad han) 45.12
of potential energy with displacement is shown in Fig, 45.2
peaking, the molecule can vibrate wih any amount of potential enery,
ial energy ofthe molecule isa continous function ofthe displacement
ibrium position,
The vibrational motion of areal diatomic molecule is pgroximately harmonic fot
a small displacement neac the equilibrium internuclear configuration (se Fig. 45.5)
‘Thus, from Ea, (4.5.12) it fllows that fora real diatomic molecule
Molecular Spectroscopy 463
that is, the force constant is equal to the value of second derivative of potential
energy V with espect tothe displacement Ax evaluated when Ax approaches zero,
In other words, it is a measure of ate of change ofthe slope of V versus x graph
‘ear the equilibrium interucless configuration, ‘measure ofthe curvature
ofthe potential well nea dhe equilibrium internuclear configuration.
old good for
quantum mechanically by solving the
resent case the solution of Setdinger
‘equation yields the following expression of potential eneegy
(0412) buat
s.a3y
where Yaa is the classical frequency of vibration (Eq. 45.10) and vis the
vibrational quantum number, The allowed values of the later are 0, 1,2, -. ete
‘Thus, the vibrational energies ae q «the molecule cannot vibrate with
any arbitrary amount of energy but with ony certain discrete vibrational energies
energy diagram (Fig. 452). The
down,
* The energy levels are equally spaced, the difference between the two nearest
levels ithe same throughout and has a value of Vay. aey
If vand (w
levels, we
AV= {041 #02} hase ~ (0+ 172) Bis
= hy,
se the vibrational quantum numbers of the two nearest enetgy
as19
Ber5y expiesed in wavenumber unit is known as vibration
bol: Giz. C= Vike“ys ig ut umoys
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From Fig. 4.5.4, itis obvious that the Symmetical stretching vibration wi
infrared inactive wheres antisymmetical and bending modes will be infaed
For water molecule, all the thre vibrational modes will be infrared active a
‘ate accompanied by the change in the dipole moment.
No change in dipole
‘moment (TR inactive)
by the sign dh
Dipote moment
changes perpendicular
; J
Fig. 454 ‘The variations of dipole mament during the three vibrational motions of CO;
Selection Rule
show that for harmonic vibration
the condition of
Av=e1 es 4
that is, the change in the vibrational quantira number is unity Equation (4.5.15),
infact, the selection rue for the vibrational transitions (see Setion 4.1),
iatomic molecule, the transition from one vibrational level to another “4
Molecular Spectroscopy 467
Since the vibrational levels ae equally spaced Eq’ 4S tos between aly
two neighbouring levels will give rae tothe ame energy change. Thus, ofly one
absorption line is observed in te vibrational spectrum of a diatomic molecule
‘Substitting Ba, 5.10) in Bq, (4.5.14), we get
(45.168)
(45.160)
[Expressing AVin the wavecuber uit, we have
ov
ap fe 45.178
fe ~ me Vt re
5.1%
Equations (5.160) and (45.176) may be used to determine the force constant
of a distomic molecule
For HCl and CO, the values of fy have been calculated in the following.
Mydrogen Chivide Prom especies, we Fin at
Ai =2 890 cm"
The value of is
po MH
mame,
(2001 Kg (6023 x 107) + (00355 kg(6023 x10
= 1618 10°? ky
Hence = 4ne’u (A?
= 46.14)? (2.998 x 10% ms
A781 x 1? kg 8? = 4781 x 1? N mt
Carbon Monoxide From experiment, we find that
AV = 424 « 10-5
“The value of sis
memo, _{(OO12kg)/(6.023 1
Ime * mg ((O012 kg)/(6.023 « 10
= L138 « 10° kg
us
Mav)? _ 4147 (138 10° (4.24 10-1?
me (602610
Hence = 4
= 1.838 10° kg 5°? = 1.898 x 107SUL 21924 1 “one By
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Energy Level
Diagram
‘anharmonicity constant. x is approximately given by hy,/4D (see Ba. 4.5.25) and A
thas a small positive value of the order of 0.0.
‘The potential energy as given by Eg. (45.20) may be written in the form stir |
to that af a harmonic oscillator (ie. Bg. 4.5.13), if we write Bq. (45.20) 28
V=(0e}) Ww [sie
The above expressions suggest that anharmonic
oscillator whose osciiation frequency decreases st
say |
The difference between the two vibrational potential energy levels is
wend leedbse (ee
Where and 0” are the vibrational quantum numbers of the higher and lower
level, respectively.
For the two neatest levels, we will have
vevel
Hence, the potential energy diference between the two nearest levels is
well dp edb eed
shyt = 25, 0+ 0")
to each other with increasing value of v Fig. 45.6)
Molecular Spectroscopy 471
‘The selection rules for an anharmonic os
transition / = 2. v"= 0, is found to have a poor intensity and is known as the
{first overtone. The transition v’ =3 < v"=0is found to have negligible intensity
and is known as the second overtone. The higher overtones ae too weak to be
realized experimentally. The energies of the observed transitions may be worked
ut from Eq, (4.5.22) and are as follows:
Wv'eleu =o Aveny,
Qvare v=o, ave2Ki
@v'ese v0, Aves
In the wave number unit, we have
Mv ere uso,
Qv=2ev'=0, avai
@v'eseu"= ave
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remperature-of the sample is high. Ths is due to the fact that the population in
‘v= evel is negligible at room temperature and it becomes appreciable at higher
tempertures. These transition ae known as hot bands as they appear only at higher
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Effect on p, Since poi does aot involve angle, we will have
Orbital
Transformation The tratsormation matrices based on p
Matrices follows.
&y @ on
1 1
ae
2-2] (7°
Bal lon
7)
EXAMPLE OF d ORBITALS (PHOSPHORUS TRICHLORIDE)
CConsideing the 34 orbitals of phosphors, we have
Bsn 29 dy = 308? 2-1
4,2 in 80s Bcos 9 i:
pin? 8.08 29
Ge=sin B08 Osin @
Effect on cos 29
The effet on cos 2¢ and sin 2p ar a
and sin 2g
Cy Operation
1
cos 219 120") =~ cs (60-29) =~ 4 cos sin
2p- 127) = cos 60-29) =~ 4 cor 29-3 sin29
. ff
sia 2¢p~ 1209 = sin 60"-29)= J cos 29- + sin 2
G Operation
a eee
Sn 49-247) = sin "299-8 0s 29-3 sin 29
my, Operation
! ~ 29) = cos 29
180° - 9) =—sin 29
Molecular Symmetry and Its Applications 579
1mm, Operation
5
cos 6r"=-29)=- + cos 29- fF sin 29
008 2000 ~ 9) =: 3
8
santa 9) x-sn("-29 =— fee 29 snap
‘rm, Operation
t B
£06 160° — 9) =— 00s (60° -29)= 5.60829 + | i029
B 1
sin 2067 - «) «sin or" -29)= {Boon 29+ sin29
With these, the effect on d o
Since d_, orbital does not involve angle g, we will have
Elds)= 4,
Ov,(4) = 2
2 Theelfects on d,s» orbital are shown in Table 5.7.
= E(sin? 6 cos 29) = sin? 000s 29= ds»
cin? zo(-2 )=-$ ~ 2
cpat vexig =i o(-Lenag- flame) =—Lay.g By
A Log
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: a 5 1 fi
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si 0-29 + Fan2g) = —Mdyy + Pa
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Mp=d ug 29 ws= (6 sg s0o9 us) ™0 = (°P)"ND
“o-vrits (oms§- nq {fom w-@ wo momio= C9
=(0us$-osm foro ure (6 ws9 09 us} = PFD
Mp ad us song uys=(6 use 9099 UN) = CPT
eye uo swona obs ome.
ee, UNO
Ors ay w unoys ap 20 say a4 ‘puo ola
186 swopwonday 91 puo Kasounuks smecnoyy
“pa mp2 = (say "f « 65002) osooous = soo 9s029u05)'o = CHINO
vfs o=(ouny hee ie 918 = (400 9800 gu) "MD = Pp)
ts iG oni} oof)
q i
%p—=d s009 song us = (6 5009 5009 Us) No = ("pO
- (conj}-sm¥Jpwomasmesmomnp =e
=(om$f-rsso! Jomo mee m9 m0 mono
pad uisg s009 us =(6 us9 soo uly = MDa
eyo p uo swoya 61's c1ae,
reo
6S aR w UMOUS ATE %p Uo Soy BM, *p uo aya
Eh = exan? sacses2bs) m= ae onnan Mo =C9%0
pba dept a (scan! + 6500 2h-)9 sa (62 us0 29/0 =
ope neh (ecws§ 4 hee 6c 59 ,08) "49 =(
4p —edcusg sas = (Oz ws gu8)"™0 =)"
opty rife = (s20n$ ses eh pap=@eme w=
“nk [om somo an oom ano x9
“p= dzusg qus= (oc us 9 wusda = Cle
revaio “pu siona a's eine.
. jeusuo
S15 gE UY Uac a %p Uo NIOND mu, p uo wo43
Aasspuoyy pow fo Y0OQH2L ¥ OBS582 A Textbook of Physical Chemistry
iiarity transformation X!AX where the max
pro
Xe (& “Ns
-ysr ir 1
where = a and y= Ji. The matix Xie the inverse of matrix X (by
definition, XX“! = £) and is given by
[* x2 ap)
0 Six xh |
ly x a)
Thos
foo 1y(-2Bx 0 By) fuse Yue aay
axe}1o ol] yse 3x -ysy|=|-a8r 0 yy
toto) lyse yy3x psy) ease thx py,
sexan=|0 ix | asx 0 “5
by yy Jase ax psy,
ip ih o
=|82 a2 0
oo 1
‘We find that the matrix A (which involves zeros along the diagonal and at the other
places distributed unsymmerc
S (ohich involves zeros distbuted symm
the nonzero elements inthe matrix S ae
blocks of the order 2 x 2 and 1% 1, eos
now the above similarity transfor
Xx" is extended tothe coresponding
(ofthe point group C,,, we get
o10) f- dp o 7
rererfi otfr=|-v3 -y2 0 -(¥, AA and
nal) i transformed into the matrix
too} (o o 1) 8h
100) p10
ware roo ileelo = of
foro} loo
01) [- “G0
ofr=| 8h 2 0 (¥, BP) a
o} ("oo 1) (ae
‘Theorem 1
Molecular Symmetry and is Applications $83
010) (-4n ih 3) oo
xtoorerfiook=|62 mz olx(22 3 ) ad)
x oke[te ole(Ge
that each ofthe original matrix representation is changed into a matix
‘nonzero elements along the diggonal and each one is factored into two
situated 252 and 1x1 Blocks, respectively, We also find tha the rest
matrices ae identical to the mati represetatons based on the translation
and T,, respectively. Thus, the abov
to changing the basis of representation from bond
“The ireducible representations play fundamental roe inthe application of symmetry
to molecular problems.
9 CHARACTERS OF MATRICES
) ofa square matix of dimension n isthe sum
69.1)
s conveyed by the transformation matrices of any
the character of these matrices.
There are two theorems concerning the behaviour of characters. These are as
fallows
If C= AB and D = BA, then the characters of C and D are identical
By definition,
coursverof C= 356, = 35 )
(oduct of two marbers is commutative)
te) (Onder of sion is ese)
dy = Characier of D (592)(a 22) (oe BE) (5 9) Ge
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