Chapter 5

Zeeman Effect
The further splitting of spectral lines in the presence of weak external magnetic field is called Zeeman Efect.
when asinglet spectral ine is viewed at right angles to the magnetic field direction then, three plane-polarised components
are seen - one Component and two a components
nComponent -a central unshifted line in which the polarisation of electric field vector is parallel to the external magnetic
field.
Components -Two lines equally displaced on either side in which the polarisation of electric vector is perpendicular to the
external magnetic field.
Zeeman Effect is of two types -
1) Normal Zeeman Effect
2) Anomalous Zeeman Effect
ANY SODIUM
SINGLET
PRINCIPAL DOUBLET

NO FIELD

MAGNETIC FIELD
PRESENT

NORMAL TRIPLET ANOMALOUS PATTERNS

b)

Normal Zeeman Effect -

The normal Zeeman effect is shown due to the transitions between the singlet (s = 0) states of the atom.
We know that, when an atom is placed in an external magnetic field B (Z-axis), the Lvector processes around the magnetic
fielQ, with quantised Z- components(L =mwhere m, is from - lto +) and with angular velocity =B. 21m
 to theretore,
the equal
so, is
by B levels number
to
given proportional
zeeman Effect.
is wave
field consecutive Zeeman
magnetic in
directly component. coincide
normal
external
Factor)
is two Am,
AT the to FIELD
Lorentz due same
the Also,betweentthe
be
with B
L, B level. of will
intensity to
called separation corresponding
moment 2m original splitting
Ls the the
magnetic L' the observed.
L' (Where, number to
m, from equal therefore, transitions
orbital , L' levelwave is compo
-by 4RmC
he together is
components
state -below
the given m, The the componen
4mc singlet
2
of
energy islevels takeeachfield
B. components 1,
0, shown since
othe
2,-1, 1 FIELD
NO
AT we of magnetic Rule- to 0,
0,1.
Am but three
interaction
energy field,energy
number, singlet -1, is
diagram ±1. allowedn to corres
a m, m, 0, with the
to
the in the both fromtherefore,
magnetic therefore, = correspon
pattern
Effect
Zeeman the wave change to
level Am,are
in
splitting
of REx- istransition
D,-
proportional
intensity Rule-transitions =t
Therefore, of given a21 splitting triplet
terms the Selection
D, lP,
l Selectionnormal
And, The a is 0 Am,
In For AT The TheFor For The 9 =
Am,And,
So.
Physics
Molecular
Atomic the
therefore,
number
Effect wave
M
Zeeman
in
coincide
normal to-
to
will
Amy proportional
splitting
due
be same
FIELD to
corresponding
splitting
is
electrons
electrons
the observed. Zeeman
therefore, transitions of of
number
number normal1/82
(d)
components quantization B (b)
state
=-3,-2,--below
1,0,1.2.3 components
is
the component evenodd quantization
a
singlet -2,-1,shown
0,1,2 since an an
ofcomponent
FIELD
NO othe with with space
but -
ieffect
s
to three atoms space
singlet isdiagram ±1. allowed then to
corresponds atoms of
=
mË mË with confirmation
fromtheretore,
theretore, 0, to Zeeman
in of Zeeman
only inonlyconfirmation
D
= are pattern corresponds
D,-Ex-isistransition level
Am,
transitions 19)Observed
Observed
splitting -Rule triplet t1 normal Separation
of
3= =2 = a c)
E.l Selection =0ám, (0)ANot -(Ans lc) Ans-(b)
B² 1/8
34 The Cor D,Eor The 15 normal And, The a) (d) la)
So, am 1 2.
 of the
spectral states
with
angular Z-
the 0) associated
nm to quantised
between 650 equal spin
its not the moment
with
splitting of and
is
splitting (s field
L
the multipletvectormagnetic
magnetic
T, places).
Zeeman
0,3 momentum
strength is
levels the the
The
decimal
between andexternal
Zeeman
(660x10-)16x100609.78x
1o
m=6pm
field. 10ms-') vector
of two angular weak
field transitions
consecutive to
magnetic
the
momentumn
4Z
magnetic (up x orbital B
Tesla3.0 around
(b)
10
pm 6(d)
pm a = the the
a
using between to ckg, to slowly
that angular
subjected
experiment
4X9.1X10-31 10-31 = x 10-9)(0.03
x due
atom precise +j)
is shown
separation field total
x of to
is the =9,11 =0.03nm
is
modeltheto -j
state
Effect of effect it from
around
is frequency magnitude
m, 4X9,1x10-31 vector causes
line singlet 16x10-19
(650x10)2Effect
Zeeman
Anomalous
Zeeman 3x10 10-19C,
A Zeeman is
rapidly
spectral splitting, the J m,
The its
The(e=1.60xB E t where
momentum
-am
=
And,
Zeeman
Effect normal Solution:
in -1.52
Tesla in precess
Anomalous
nm 12
(a)
pm 8(c)
pm (d) atom
nm. Solution:
Zeeman 3x10 seen
660 Ans:
a 0.03 have U,=m
In a An S angular
vector
4. The atom.
We
3
 Physics
Molecular
Atomic is J the
shiftdifferent
or
the separations
so, for +2.*3
B different +1 1
to relative
proportional 2 2/3 -2 / 1
is
the
splitting -12 -3/2 -/2
M
that
directly
Zeeman
means 0)
=
Factor) Aj 3
is the This if 2 2 3
AT forbidden
levels.
Also,that
Lorentz
-JB
, B is 1)
AE912m2 here different
level. +
(2j
AE 2mh
=9) called is
note
original transition levels
for
is to 4
my=9,m' the pointdifferent
L
Zeeman 2 2
(where, =0
fromimportant alone.
is m line) of
L' level factor) g-factor to (D, No.
by = =0 -
given =e9, An
e8 4mcm, lande +ZU2)ts(s+1)-I+1)
'Sy (=1s=jj
=)
below
takeeachB. the my Sodium shown
is tield - (But ’
levels (8 by Psyz 2/G+1)
a7 we of magnetic g, determined0,E1of
is
energy number,givenenergy of
field,
magnetic linesand diagram
value =
in
the the are Am, and D, line)
the
wave
change 1 Terms level
in to hecause -
Rule (D, =know,g,
splitting nnrtional levels D,
of Example-
5 splitting
terms the Teeman
calection
aaFor is le
36 The Io AT ?P We The
 37
Effect. 62
62 anomalous
Zeeman
Effect.
=0) Zeeman 9,my =0)
line. gM, 6/5 2/5 -5/5 1/3 -1/3
AJ Aj
if D2 anomalous if
forbldden
for M, B/2 1/2 1/2 B/2 1/2 forbidden
obtained (t/-)
1
to +1) 1 to
ls components due is L(+1)
transition I(l due
transition
be -
will+s(s+1)
2/(+1) 2
be
will 1) - 1)
0 and6Zeeman splitting levels
m,=0 splitting+ +
=
=1+-U+) s(s (
m, 2/
the Zeeman +
to to the JO+1)
=0 therefore, =0
(2j+1) therefore,
m, line of =}/=)2
(ButD, components No. m, components 9,
=1+
(But
±1 for
obtained
component
state g, Dya(l=2.s=/=)
4
1 state
0, doublet below obtained.
component
= =0, doublet
Am, a
the shown
is
components
rt to to Ra(=1,s Amy the
components to
the
transitions corresponds
doublet
is is Tt to
to -Pyz diagram the corresponds doublet
transitions
D,
corresponds from
Zeeman Terms
to -Pyz
Example-Dsj2
corresponds from
Effectfor
Zeeman = 1 Example2Da/2
is level Zeeman
rule transition for Amy=tl is
4
are =0 Am,
splitting rule transition
Selection 6
There are 0
Selection
Am And, The The =
There
Am,And,
The
Physics
cular 5'55"5-5-15/5
2'2
22'2
Mole 3'333 gM15/59/5 -2/3-6/3
6262 3/5 -3/5-9/5-15/5 6/32/3
9 Effect.
Atomic 3 0)
M, 5/2 3/2 1/2 -1/2-3/2-S/2 3/2 1/2 -1/2-3/2 Aj= Zeeman
3
9 if
forbidden
15 anomalous
*****.eene.
5 1(l+1)
13 22
(+j.
.-D
2'2'
3 is
transition to
1 due
- 1)
3 31
5 0
be
will g,=1+U+)+
1)
++
((
= splitting 2j
m,
g 4 6 to
0 the
Zeeman
1) = therefore,
+ m,
(2j (But components
oflevels +1 obtained.
below component state
No.
4 Dsa(=2,s=}/-9
5
shown
0,
= a triplet
Am, components
the
is Tt to to
is
diagram thecorrespondstriplet
transitions
to
Corresponds from
Zeeman
level P
Terms
for =t1 -D,- is
splitting rule 12 anstion
Selection
are =0 Am, Example
The Ihere Ano,
am
 12
T330-3"33
o-714 6
M14/6 -7/6 -14/6 3/2 -3/2 Effect. 8
m0) 8 434
147 A/ Zeeman
if 63
forbidden
anomalous 12
2,1,0,-1,-2
(+/)
1,0,-1
is
I-0,=1+4Y)+s(s+1)
0+1) 32,10,-1,-2
transition to 3,2,1,0
due
be 2/0+1) (+/
m,=0 will
6 3 2
splitting 3
ofZeeman
levels
(2j+1) to levels
my=0 the
(2j+1)
Zeeman
therefore,
No. 2)5 (But components
3 t1 obtained. of
below state No.
= =
1) =0, component 3)7
5
1,j 1,j shown a triplet
Am, the 2)
= = components =
2,s 1,s is is n to to 1,j 1,j
diagram transitions
the correspondstriplet
= (= to = =
Terms
(l correspondsExample-D,-P
2,s 1,s
D, PP, Zeeman from (=
level =
Zeeman
Effect for Am,=t1 is Terms (l
splitting rule transition D, P,
9
are
Selection
=0
The There And,
Am, The
Physics
Molecular
Atomic
gM,12/3
8/3 -12/3
4/3-8/3 6/23/2 -3/2-6/2
0)
Aj=
-2 -3
M 3
if
forbidden
is
transition
0
=
m,
to
0
=
m, components
(But
±1 obtained.
-below
shown
diagram component
0,
= o
the
Am,components
is Tt to
is corresponds
transitions
the
to
corresponds
Zeeman
level for
split ing rule15
=t1
Selection
are 0 Am,
The There And,
Am
 Chapter6

Paschen Back Effect

inthe Zeeman Cfect. the external magnetic field is weak as compared to the internal magnetic field generated by the motion
of theelectron(Spin and Orbital motion of the valence electron). When astrong magnetic field is applied then the separation
between the Zeeman components become very larger than the separation between the multiplets of fine structure
componentsand the anomalous Zeeman effect changes to Normal Zeeman effect. This conversion of anomalous Zeeman
EffecttonormalZeeman Effect in the presence of strong magnetic field is called
Paschen Back Effect.
Asthe external magnetic field B value is increased, the coupling between the / and B becomes stronger than the coupling
s in this case, the precessional velocity ofJ around Bbecomes larger than the precessional velocity of Land
between Land4`
`around Therefore, the coupling between Land Sis partially broken down and Jis no longer fixed in magnitude. As the
onetic field becomes further stronger, the coupling between Land ` is completely broken down (L and ` decouples) and L
d` starts independently precessing about the magnetic field Band the spin -orbit interaction can be neglected.
B

S S

moment with the external magnetic

magnetic moment and spin magnetic
Therefore, the Interaction energy of the orbital
ield is given by
esplitting in the energy levels is given by-
AE =GL, +2 2m S)B
-2m,
+ Zm )B
AE =m"m2r
In terms of + 2m,) =
eb (m + Zm,) L'
wave e number, AT =hc 4 mc (m(where, L' is called Lorentz Factor)
Fora given take=L'
magnetic field, we 4TmC
 46 co
45 3
g
(Be ce
autsd
e m
We
Paschen Back Effect
presence of
Example 2p’ 2s
sodium (P/nan -2S,2) is splitted into 10 lines. In the Therefore,
A
and D, lines of are as follows
In the weak magnetic field, the D, interaction can be neglected. Therefore, the splitting in P and S
strong magnetic field, the spin-orbit
m
No. of Strong 77Ly (m +2 m,) Drawt h
Terms
Fleld levels
(21+ 1) (2s + 1) 1. sodium
11 2,0 Solutio
1
Rp 2 2 1,-1
11
(=1,s = 2 2 0,-2
Where
-1
11

Term
2 11 1,-1
2
(t=0.s= 22
two levels for
table but actually it splits into 5 levels because there are
The P term is splits into 6 levels according to above shifted by the same amount from the original level.
which m + 2m, is equal to 0. Therefore, both these levels are
Selectlon Rule - Am, = 0 ( component)
Am, =t1 (o component) and Am, = 0
(M,+2M,) M M (t=2.5
2 1/2

1 1/2

0,0

-1/2
The

1/2

1/2

-1
-/2bt

2.
Th
is

Strong-Field Pattern

ifasonline.com fase
 internucleae
af molecule electronie
frequency which
graph afrom
the same lines) of
the and the shifted theory
the in
then occurs the (vertical
shown abovel
It of is the
them)
changes. levels which
resonance then
Bards.
Wrak bandsbranches shown
between energy bandand
moment Molecules) 3w weak overtone)..etc. graph
the molecule. two fundamental
vibrational
separation
then, origin) and are the
Spectra dipole
molecule (Hetronuclear
the
(Bard
fromo'There of
part
Wrak
Bards
Sw
the on
relative
hence, between on. of overtone),
'3a'(Second a
incident Bard shifted theory
so is Pure-Vibration
(Spectra)
the 2w (which
theand of present Fundamental and
the
vibrationtransition radiation) is overtone)..
Vibrational-Rotational
changes
changes
be
which see below Fundamental
shown Bard
R-Branch will
should
(Infrared line)
of
molecule the we
frequency
molecule all levels)
to '3a'(Second
(vertical
due
moment
-
radiation
W
of 2afirst graph
the Rotation) First
vibrationaltheory
thethe arises Vibrational ofthe
in Dipole band parts.
of with spectra
(atoms external Spectra Rotational overtone),from
atoms
matches +
Changing (Vibration P-Branch Spectra fundamental in
graph the
shifted
10
Chapter vibrates
the
-rotational the to
this attached Pure
the
explain
Vibrational
Spectra
waveradiation.
absorbs
the - to '2w'(first are
Condition
due Graph
between
molecule contains
graph
This understand
electromagnetic is
vibrational Pand
'R
which
branch. will
energy
level. Experimental
vibration (branches
Necessary from bands we
a distance all
When shiftedwill
The This weaklevels of
We First
Physics
Molecular
Atomic of but
fundamental
band
vicinity
followed.
the
in strictly
vibrating
probability.
not
1is
are Le.
atoms awavenumber
be decreasing
means
Av
That
because
with
terms but
quantum
no. on.
order onlyso possible
and
higher should
4a).. also
1e(rlav;p.lnaotiabriv
frequency;
V’vibrational
(neglecting 3a, are
there
o)-ka
v VEU
2a), so
on
2 Spectra,
on and4
dr2 e)
a=
(Where observed
Series
-Taylor
function k=
(Where,
r-Te)r
/, Vibrational=v
also v=3,
in k(r-)
u)=%+2massReduced um-t
(v+)
s0=
were
Purebands
2,
tiPotal en posimt eopane) no.,
wave
of
theory t4 V
weak F0 0
+3,

to
v
Rules
Selection BAuy,
1,+2,
the opand dr oftems e
from
Transitions
H y
5
Shifting
IA) (aof
) (2) Initially,1)
Important
(Points: theWhen case, the The
With constant
decreasesAnharmonicity X
Anharmonicity
Considering
G) Vibrational-Rotational
Spectra
Weak
eroy(Fundamental
excess vicinity
the littile
molecule
receivesthe increasing =
gap bands energy (v+)- higher shift
there as of
b/w lines the
the of
were Band) vibrational value power lines
the (w, was is mean
explained converted
two 2u, only of terms (a,
corresponding position. 2a,
ve30,) v,ax,
'a energy quantum the
(v+/2) in 3a,
by to the
(wavenumber) the second .)
isthe corresponding
kinetic taylor Then,
plained
elsrelaxation to VeO no. is
the due
'a' increases.terms series
es but energy Anharmonic to
Anharmonicity.
expansion
byin nogap starts
dering weak
selection between of to
as the the dominating
the bands highest
atoms ofpart
al rules the potential
Anharmonicityof
icity.
(av vibrational the
two thus,
potential
cannot
successive
1, energy
+2, level, be is
energy
considered
no. ±3, energy it gap neglected).
(v) t4.) dissociates b/w curve
. the
with levels when
comes
into two
creasing so, the
we the successive intoatoms
got individual the
obability. picture
do
only not
energy
one atoms vibrate
ln
bu les
an
ne.com Iherefore, levels, B=
As, value
moment of AsThe rotational
F(),interaction
add Here,the But to F) So, In In In
vibrational(whichVibrational Expression Wave
vibrational the the the Pure Linear this, AGg-y=G(v)-
G(General
o) number
interaction
=BocB is of
different
vibration +waveVibrational
expression G(v) Vibrational
is
we
rotational independently.
G(v) levels Diatomic attached
inertia energy +
must number
= Rotational
quantum
between due difference
between
for should w(v+'/)-
constant of written Spectra,Non-Rigid level). to +
have different molecule to Rotational
the
between external in
a vibrational be Vibrational So,lower Spectra
mean number considered above
decreases decreases wavenumberMolecule, in (When
vibrational increases vibrational radiationwx,(v vibrational
thisAbsorption
value is v'=1 V'=1 -
increases, and wrong + case transition two
of as because Rotational
+
with wavenumber Vibrational Energy
rotational states. vibrational and rotational because /2) is energy
increases & (In given Spectra,
hence, the rotational Infrared c) F) is
rotational +
should from levels
internuclear levels of
Bj( level)
as
constant quantum
rotational
= by = is the 0h
in thregion)
e o(v+)-
+ be BJâ+ given well -
v. is levels molecule
to to
- levels folowing 1)given asthe vh
for Thus, 1) by 0 J"= 2 J"=3 -
J'= J"=1 J'=4
number
constant is(Neglecting Rotationalhigher vibrational
distance are not by -
given a 'B' - Dj°g is
attached
considered.reason ax, making
which increases. rotational
vibrational decreases.
between (v+ + levels level)
- the 1)² transition
determines to vibration /) of
the An energy
a
So, the molecule,
state vibrational
interaction
the two due J'=0 J'= 1J'= 2 J'=3 f'= 4 level from
- the
spacings
interactionatoms to both(Which the
energy
between
centrifugal lower Molecular
Atomic
Physics
are
increases is
between lies changing. rotational
attached
levels.
in the force
the and vibrational
So, and
the fact in to
ener8Y
therefore. we comparison the
rotational that cannot higher
level
the
 AC leveltransition
KCuDo(v+/)-wx, Where vibration)
It=, B,Spectra
constant Vibrational-Rotational
AC(v.) AC(V,)=C(V,)
c(V) -Now,the G)Now, can
(v,) Le. after c, be
= = V F)+ corresponding shown
and including is
V, o(v' = a
+ j" constant that
is (v+/)-
By/'G'+/2)-ax,
+1) the between interaction, -
lower tothat B,
the (Where
rotational (v+/) the B-a,(v+/)t
depend
wx, wave separation
( two (v+
Byrj'"Û" - +/)+ (Wherelevels is
no upon
energy /2) G(v) 'r the
+ is at the mean
+1) j' BJâ
given +B, +
level the is the
B,fU shape
+ JQFO) minimum value
becomes,
attachedhigher theby1) +
+ 1) of
1) difference the of
rotational (Where of
- to internuclear
a(v" the potential
the
lower in C(v,) potential
+/)+ energy
Cvalues
energy
energy = distance
level G(v) energy
ax, of curve
vibrational
attached two +
(v" 3 4 curve in
vibrational
levels F()) (a, the
+/)-Byy"è" SV'=1 (B,
to < vbrational
(1) V"=0 level
the B)
e.
L.higher and
V) state
B,
energy is
+ the 'v
1) vibratian rotatie during
67
 decreasing.
The As, AC(v, weThe And,
increases. The left Now,
AC(v.AsAC(
) V=0,1,2,3,4.
,) Put Swhere, Now, spacing
o, j'j-j" increases. As But AC(v.
" ) AC(v.
) ) tPhuet So,j Where, For knowTotween Where F,
s
the 38,- on B, = R-branch, Theory now ,
e.com soacing side B for increase,multiplying < = = = value 1,2, j" the
B, ons
,nand wavenumberthe s
here < value j"= Bn’ =
of of we(branches)
= = P-Branch, Bgn VoVoVo Bn
the both B,v, v,=-1j=j" 1,2,3,4 between + ofj' 3,4, 0,1, selection
4j P have
between + of f'
j" = +j"* B,y(" +
ByQ" . and fixed are
reference the B-+" B, +ve By, B in 2,3, = R the
in term (By, terms j' -j" the
terms (Bñ- ( " terms . Aj=-1 the by -B . . rules
branches rotational
betweenerotational
the ariound
Absorption/emission the - wil + +
Byr twO 3,3B By) 3j" 1) of =1for transition
twotransition j" Byr)1)0") of - wil (" j"
j" 1; dominate -
+ rotational
=f'
t. the of
and wil successive + +2) in levels and,
successive be - in be 2)
>j"(3Bñ
equation constants
level j" j" equation Bn - =j" Vgpure
have -v e (By Bñ(" ve B,yn - (attached
v:
and (Because B,nj"(" transitions
+1 =
vibrational
levels the + levels since -(j"2 (1), corresponding
olv
By) 1)j". +(1), By)
in
negative in the there +j") to+2)-wx,(v
the + + - vibrational
the levels transition
P the 1) Ai
Branch contribution
R- is 2B, vibrational
P-
contribution. only =
branch branch +1 to
a higherthaned which
slight
slowly slowly of levels +'/,)-o(v"
Therefore, s
thidifference by is
term which fixed
increases decreases v,
Branch R is and lower as
AC(V,)) negative. between we the
as as now,
have vibrational +1/) reference
the starts the
Bandhead B already we
rotational rotationalTherefore, and wil +
slowly levels
ox,(v"+1/,) so
Molecular
Atomic
Physics
B) fixed). look as
quantum increasing quantum AC(v,j) into
respectively. to
study
the
towards starts theory the
number number rotational
slowly of
i the " the
 69
Vibrational-Rotational Spectra

(Trick to Remember) -
In General,
(AC)PR = V + m(By+ Br) +m² (B- B);
where, m=-j" (For P- branch)
and, m=j" +1 (For R- branch)

Rotational levels is ignored

If the interaction between Vibrational and
Then, B =Bu, = B
(AC) = V + (" + 1)(B +B)
(AC)R =o +2B((" +1)
And, (AC), = +(-j") (2B)
(AC)p = , 28j"

mo

positive values and in P- branch, the line

Conciusion - In R-branch, the line spacing slowlydecreases as 'm' takes on increasing
spacing slowiy increases as 'm' takes on increasing negative values.
j" term) is always seen in the
Asmall tendency of head formation (where quadratic j term starts dominating over linear
R-branch and a small tendency of degradation is always seen in P-branch.
the lower wave
We can also say that the rotational- vibrational bands shows a small tendency of degradation towards
wave number side Le
number side i.e. towards red and shows a small tendency of head formation towards the higher
towards violet.

Diatomic Molecule as Symmetrlc Top

In excited states, the symmetry of diatomic molecule gets disturbed &there are chances that its M.O.l. along the internuclear
axis I 0.

So here, C(v,) = a(v+/2)- ax, (v + /2) +B,J ( +1) +(A - B,) 2²

Selection Rule -
Ifl = 0,Aj = +1
IfA # 0 4j = 0,#1
Again, ifl = 2=j =0,1levels wil be missing (From the theory of Pure Rotational Spectra of Symmetric top molecules)
Now, 4C(v,j) = C(v'j) - C(v",j)
=o(v' +)- wx,(vt 2) +Bjâ +1) +(4- By,) 2² - o(v' +1/)
+ox,(v'+ /,) - B, j"Û" +1) -(A- B, )22
)22
AC(VD= Vo + Byj'â +1) + A- By,) 2² - B,nj" G" +1) -(4-B,.
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 Atomic Molecular Physics
70
the rotatoe
(Where v is the wavenumber of the pure vibrational transition wthich is fed as the reference so as to study
transitions (branches) around it
and, v, o(r4)-ux, (v+/)-)tan()
For Qbranch, &j 0 f " mj
- AC(v.) =v+ By/Q +1) - Byir +1) +(4- B)2- (4- B)2
8C(v.)t,+P(B-B) 4+ j(By-B,)-28,-B)
w
5C.(V.) For Qbranch is very small because there ss sigtt 6ference between By and By&the lna of Gbranch
be very close to the fundamental band (or band origin), 5o, they cannot be seen separsted esshy
Take the case, A 2
So, Aj 0.+1
jm,1 levels are missing
MA=0, then Q-branch willbe missing, as, aj m0 wil not be an allowed transtion rue anmore
Distributlon of Molecules in Vibratlonal levels
The number of molecules in vvibrational level is gven by -

AG Gv)-G(o)
N-No.of molecules in the ground state
N, No. of molecules in vbrational state
where, Gv) u(v+ /)-(v+/

1000 K

300

012 3 4 10

Distribution of Molecules in Rotational levels of a particular Vibrational level

Rotational Partition Function

-+1)e-fulr d

Let j(+1)mx

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 Vibrational-Rotation al Spectra

300

CO

10 19 20

NhcB(2je1)e -FU)
KT
For the maximum populated rotational level

=0

e+De-/j*)%ar) =0
L-2
And, if Bf Jmax
And, I t Bl»jmax T

For examnple- CO Molecule (Absorption Spectra)

CO

300K

P(7) Vo R(8)
P
R
1000 K

P(12) V R(13)

Important Polnts -
(1) As
temperature
(2) The intensity of increases, the band extends on both sides because more
maxima both branches move
in lines in
because jma increases as farther away from va (Band each branch appear.
(3) As temperature increases oriain) and occurs at higher J
temperature increases, height of intensity maxima
the
number of rotational levels. decreases because molecules are now
(4) The inequality
between the intensity of the two branches become less distributed to te
marked.
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Chapter 11

Electronic Spectra
There are various possible electron arrangements for a given molecule which form different patterns of
allowed electronic
states. For each of the electronic states, there is different dependence of molecule's energy on its
internuclear separation.
The electronic spectra arises due to the transition between the different electronic states.

D
MOLECULE'
ENERGY S

U=0

Vo

D
3
(T,-T)
mVe

U=0

INTER-NUCLEAR DISTANCE

potential energy curve.

Each electronic state of the molecule has a different
F")
V= (T-T") + (G'- G'") + (F'"- transition
(Where'v' is the wavenumber of the between two electronic energy levels)
level
vibrational energy level associated with it and F is the rotational
(T' is the higher electronic energy level, G' is the
attached to the G'vibrational energy level.)
vibrational energy level associated with it and F" is the rotational level
(T" is the lower electronic energy level, G" is the
level.)
attached to the G" vibrational energy
Electronic Spectra
Electronlc Vibrational Spectra - 75
Take, T-T = v, (We have fixed the electronic transition as the reference for studying vibrational
associated with it)
As we know that each electronic state of the molecule has a different potential energy curve, G' and G'" corresns
vibrational levels associated with different electronic states and so have different and ox, values. Also here, C'to
larger or smaller than G'".
Ignoring the rotational structure of the individual bands (F' = F" = 0). Then the wavenumber is given by
V=v, +la' (o+/) -a'(v +/)-a'(v" +/)+ o'("+)
For electronic transition, there is no restriction on the change in vibrational quantum number 'v
So here, Selection Rule - Av = Unrestricted

Electronlc Rotational Spectra

The wave number for transition is given by
v= (T;-T") + (G'- G') + (F' - F")
Take,(T-T")+ (G'- G")= Vo
(We have fixed the electronic transition and the vibrational transition associated with it as the reference for studiee
rotational spectra associated with it)

v= V + B,j'â' + 1) - Byrj" (" +1)

Selection Rule- Aj= #1
For R- branch, Aj =+1,
VR = V+2B,y + (3B, - B,r) j" + (B, By) j"t
For P-branch, Aj =-1,
v = V - (By +By)j" +(B- Byr) yyh
Difference between Electronic Bands and Vibrational- Rotational Bands -
1. In an electronic transition, the rotational constants By, & Byn belong to different electronic states and so
they are widel
different Le. (By -B) has a much larger value than that in the case of vibrational - rotational spectra.
2. In electronic transition, B, and Byy belongs to different electronic states, so (B,, -B,) may be (+) or (-)
whereas
vibrational -rotational spectra (B- By) is (-ve)
If By - Bn= (+) ve
For R-branch
Now, here both the terms jhh and '" have the positive contribution. Therefore, v starts rapidly
diverging towards the r
side of the reference transition level Vo
The spacing between the two successive levels in the R- branch rapidly
increases as the rotational quantum numbe
increases.

For P-branch
As increase, j term will dominate and since the contribution of this term is
converging. positive. Therefore, v starts o
The spacing between the two successive levels in the P- branch rapidly
increases.
decreases as the rotational quantum numpe
If (By - By) = (-)ve

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 Atomic Molecular Physics
76
ForR-branch Therefore, v starts rapidly
increase, 2 term will dominate and since the contribution of this term is negative.
As /
converging.
successive levels in the R- branch rapidly decreases as the rotational quantum number J
Ae soacing between the two
increases.

For P-branch
the negative contribution, Therefore, v starts diverging towards the left side of the
Now, here both the terms j" and j" have
reference transition level vo. number J
levels in the P- branch rapidly increases as the rotational quantum
The spacing between the two successive
increases.
tendency of
violet - degraded bands are observed in electronic spectra and a strong
Conclusion - Both red- degraded and
is (+)ve or (-)ve)
on (B, -Bn)
head formation is seen in both Rand Pbranch (Depending
Trick to Remember -
In General,
y=V+ (By + B,r)m+ (B- B)m²
Where, m =-"(P- branch)
m=j"+1 (R-branch)
vertex (band-head) is given by -
This is the equation of Parabola whose
dm
0=0+(B + B) + 2m(B,- Bn)
Mhead 2(6,-B)
- B) mead
Vhead Vo + (By + B) mhead t (By
Put mheag in the above equation
Vhead Vo B-B) degraded band.
degraded band and negative for the violet
Now, Dhead - V is positive for the red

24

20 -
16
12

-8 -8

-12 RED- DEGRADED BAND

-12
VIOLET- DEGRADED BAND
-16
-20
24

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 Electronic Spectra
FRANK CONDON PRINCIPLE (Electronic spectra)
According to Franck- Condon principle - An electronic transition in a molecule takes place so rapidly ascancompared to te
be consd
Vibrational motion of the nuclei that the instantaneous internuclear distance and the velocity of the nuclei
remaining unchanged during an electronic transition. So, according to this principle, the transitions in which internur
froe
distance does not change during the transition have the maximum intensity and the transitions which deviate
Franck -Condon principle have less intensity. Hence, the intensity of that transition is maximum which is represented h
straight vertical line.

U=3
U=2 . . . L
U=1 - . A l . .
U=0 **