v -- Vo, +o

3
A (4 3 I)
v 3X 2- 2X 2 =Vo +L \v
! - I I
r 4. mi - 2 ➔ 111 _J= -2
I
!
I

_
V -X
,
V3 - Vo +o 3 2 -+ 2X
A'

2
- (4 I I)
=t /
o 3
5L\ v
+-
I
_
I
if l I
! 5. 111_j=~2 ➔ m1=2
!
v()+Av(-;x~-2x~J=v()-:Av
I

I v4 =
3 I
6. m- = --
2
➔ m-=--
2
:, J

, 'A (
- 4 x 3 + 2 x ]) =v0, -L \v
v4 = v 0 +i lv
3 2
' 2

I
I
I
I
!
Th us, the D 2 .spe ctr al lin e of sod
splits into six spectral lines, in the pre
Example 21.1. If a 50 00 A lin
ium

e ex
, shows anomalous Zeeman effect and
sence of external magnetic field.
hib its no rmal Zeeman splitting of
1.1 x l o-3 A, find the field strength~
x 1o- m
7
Solution : Given : .,i = 5000 A = 5
13
L\J = I.I x 10-3A = I.I x 10- h

A2 eB
Since · Li l= - -
c 4nm
= Li l 4nmc
1 ... 8 l 2e
I -
1' I x I o-JJ
(S xl o-
31

7 )2 xI .6x 10 -
I9
8
x 4 x 3. 14 >- }. Ix I0- x 3x 10

i'
= 9.43 x 10-3 T
 ATOM IC SPEC TROS COPY
97
an
Exam ple 21.2. Calculate the Zeeman shift observed in the norma l Zeem
effect, when a spect ral line of wnvc len2th 6000 A Is place d in a magn etic
field of0.6 Tesla. (Given elm =1.76 x tofi C kg- ).
1

Solut ion : Given : ,i = ·6000 A= 6 x 10- 7m

= 0.6T
B
elm = 1.76 x 10 11 C kg- 1
The Zeeman shift in 'terms of wavelength is expressed as
A ,i = A2 eB
c. 4nm .

A ,i = (6 x 10-
1
>2 x 1.76x lo11 x 0.6
3x108 x4x3 .14
Al= 1.01 x 10-11 m = 0.101A
Example 21.3 A certain transition in an atoin of wavelength 4226A when
rn
observed in a magnetic field of 4 Tesla exhib10its a normal Zeeman· patte
Calculate
whose components are separated by 5.6 x 10 cycles per second.
the value of elm.
Solution. Given : l = 4226A = 4226 x Io-10m
B = 4T
Av~ 5.6 x 10 10 cyc_les per second
· eB
Since Av= - -
4nm
10
e 4~v 4x3.1 4x5.6 x'to
-=
m Jj 4
e
.- = 1.759 x 1011 C/kg
m

. 22. PASCHEN BACK EFFECT

Paschen-Back effect is the splitting of atomic energy levels in the presence
;ijf a strong magnetic field. This effect is a limiting case of Zeeman effect. It
occurs
the
j Jten. the external magnetic field is sufficiently str~ng enough to disrupt
,:· ➔ ➔

ctoupling ·between L and S .

.; As already discussed, Zeeman effect describes the splitting of energy
levels
Jg5the presence of an external magnetic field. If the magnetic field is sufficiently
. . ➔
~
ar
weak the coupling between orbital angular momentum L and spin angul
➔

momentum S is very effective and they lead to resultant total angular momentum
➔ ➔ ➔ ➔
J · The vectors L and § precess about J , which further precesses around

__J
 1
98 RELATIVITY AND SPE CTR OSC OPY

field ➔
the extemal magnetic. . F'
B , as shown m
is large enough, it disrupts the coupling betw1g. 22 •1a· But. if the mag.netic field
een the orb1tal and spm angu 1ar
momenta , and the vectors ➔ L and S ➔
precess m• d' ~d 11
1v1 ua Y a
bout the external
magnetic field, independent of each other, as shown .
in ~ig. 22.1 b. Thts effect
is called the Paschen-Back effect.
E(weak magnetic field) 1(strong magnetic field)

"'J
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\

(a) (b)
Fig. 22.1. Paschen-Back effect.
Note : The tenn strong field is a relative one, since the
field strength required
depends on the particular spectral line being investiga
ted. The splitting of a
spectral line can be explained well by Zeeman effect
provided the splitting is
small compared to the energy difference between
th~ unp
Ue., levels in the absence of field). This generally occurs for low ertu rbed levels
fields. At higher
fields, Paschen-Back effect comes into picture. The field
must be strong enough
to produce a magnetic splitting that is large compared
to the splitting produced
' I by spin-orbit interaction.
The energy due to interaction of the atom with the stron
field is composed of : g external magnetic

(1) Energy due to precession of ➔ ➔

L about B (6.ELB)
(ii) Energy due to precession of s about B (6.EsB)
(iii) Energ
y due to interaction between ➔ ➔
L and s (~Els)
The
thereft third
th
factor 6-E ·
I. LS _
1·
1s neg 1g1'ble m
·
compari.son to first two factors·
ore e tota mteraction ener gy of t · h
field can be expressed as : a om m t e presence of strong magnetic'
M= MLB + MsB
or
M= g, µBml B + gsµB
ms B
 , ,, n, '"'' ' • . .'!. -=-_,.-------;---_ ,,
....\ l\.'\\f , ~ "i'.'·;

SUMMARY
• Atmak s~tnl...~~l\\' \l~\ls with th~ inttwnct,on ot' tlluctt"'"'"·""~tlc
~ti,tk'l~ Wl'th ~t('\j\"~-
• At\'llllk- ~nnu "'f ~\t~.h ~l~tnc1,t ls \.mh1uQ~ h~nc..'C it Is ttu mod n~ tht
fi~yt'rint \\f ~ ~t\1tn.
• Eltttl"l,main etic Sllt'Ch·tnn is tho tlntit'tl rungo of ntl possihlo
d«m"'lt~ttetit' rndifttions. It rot'@.~ fl-on, high w,orgy gnmmn mys to
lo\,.. ~~y n\dk, ,,1\\"e~
• 1)--pes of Sptttra : A~'QtPtion spootrn and Etnission spectra.
• _.\~ion si->ectnnu is spt'ctnun of elootrotnngnetie rndintion trnnsmitted
~~ s substan~~ showing dnrk lines or bunds due to ubsorption
~t spec-ific ,,-a,~ltutgths.
• , Emission sptttrun1 is a spectnuu of electro1nngnetic rndintion emittl'<i
.. ~
bl' SOUl\.'C.
• Quntum theory of light defines the particle nature of light. Light is
made up of tiny pmticles or quanta called photon~ ench having energy
E =hu.
• Plaoto11 is a discrete bundle (or quantwn) of electrotnagnetic (or light)
energy~ which is .never fulmd at rest and travels with the speed of light
in vacuum.
• Early atomic n1odcls include the Dalton 1nodel, Tho1nson, model,
Ruthecford model, 13c,hr's n1odel etc.
• .IIGVs model postulated that electrons revolve around the nucleus in
circulv orbits. Only those orbits are pern1itted for which angular
momentum of electron is integral rnultiple of h. The energy is emitted
when electronjun1ps from higher orbit to lower orbit.
• Electron spia : Apart from the orbital motion of the electron, it also
spins about an axis passing through its centre of nmss.
• Pawl's exclusion principle states that no two electrons in an atolll
can have same set of all the four quantum numbers (n, /, m1 and ms).
• Orbital •n&ular momentum is the angular mon1entu1n possessed by
an cl~tron by virtue of its orbital motion around the nucleus. Its
m~1utude and orientation are quantized.
• Sptn angular moment •
. t b . · um ts t11e angular momentum possessed by nn
e1ec rot· n d Y virtue of its spin motion. lts magnitude and orientation are
· ·
quan 1ze .
 PY
RELATIVITY AND SPE CTR OS CO ATO MIC SP EC T

ntum of an ele ctro n in an ato m is the vec tor sum

~ I ang·ular mome · ang ula r mo me ntu m and is
I ar mo me n t um an d spm
•
fota
·t orb ital ang u
of IS ➔ ➔ ➔
expressed J =L + S
.. . . SH OR T AN S
m terms of the orbital ang ula r
Vector model of atom 1s an ato mic model ➔ I. Dif fere nti:
• ➔
S of the ele ctro ns, wh ich 2 Wh at is e
momentu m L and spi n ang ula r mo me ntu m vis ible lig
➔ ➔
en L and S, bot h in the pre s-
describes the intr ica te cou plin g bet we fields. 3. Dif fer enti
tic
ence and abs enc e of ele ctri c or ma gne 4. Wh at is a
vec tor model of ato m are:
• Q~antum numbers ass oci ate d wit h the 5. Wh at is I
ind icat es the ato mic she ll and ene rgy
(,) Principal qua ntu m num ber (n) : It 6. Wh at is c
of electron.
7. Wh ~t is t
(ii) Orbital quantum nu mb er( [): /=
0, I, 2, 3 ..... (n-1) and L= ,JI (l + 1) h. 8. De scr ibe

✓3· . 9. Sta te the

. ,.- -- -
h.
(iii) Spin quantum num ber (s) : s =½
an d S= '\Js (s+ 1) n= 10. Wh at w e
2 11. Wh at w,
f
ntu m num ber U) : j = I ± s and
(iv) Total ang ula r mo me ntu m qua 12. Wh at is
J= ,Jj (j+ l)h . 13. Wh at is
qua nti n
(m 1) : m1 = - I, .... 0, ... / and Lz = m/z
.
(v) Magnetic orbital qua ntu m num ber 14. Wh at is
I I dep end
num ber (ms ) : ms = -- , - and
(vi) Ma gne ti~ spi n qua ntu m 2 2 15. Wh at is
16. Wh at is
h h
Sz= m Ii= -- _; 17. Na me t
s 2' 2·
= m/z 18. Wh at fa
(vit) Magnetic tota l ang ula r mo me
ntu m qua ntu m num ber (m1): Jz
19. Wh at ii
ed the pre sen ce of ele ctro n spi n
• Ster? Gerlach Experiment con firm . 20. Wh at d
and its spa ce qua ntiz atio n.
to wh ich the orb ital and spi n 21. Wh at i:
• LS Coupling : It is a sch em e acc ord ing
bin e to giv e res ulta nt ang ula r 22. Wh at c
angular mo me ntu m of ele ctro ns com
momentum in mu lti- ele ctro n ato ms. 23. Wh at a
l lines into two or mo re clo sel y
• Fine structure is the spl itti ng of spe ctra 24. Dif fen
freq uen cie s and wa vel eng ths . It
sp~ced lines hav ing slig htly dif fer ent 25. Wh at
spi n and orb ital mo tion of the
arises due to the inte rac tion of the onl y ir
• e ectrons pre sen t in the ato m.
eno n of spl ittin g of spe ctra l line s in
the 26. Define
Zeeman effe ct is the phe nom .
I
I, I •
Presence O f
p ext em al ma gne tic field.
ng of ato mic ene rgy lev els in the
ESSAY T~
r
p aschen-Back eff ect is the spl itti 1. Expla
resence of stro ng ma gne tic fiel d. are th
 101
ATOMIC SPECTROSCOPY
' ' '. ' ' . . I., .
. .· .. . ' .. ' ' QU ES TI ON S ~ •
•

·.
•
! • • I

• •
' •
~ •

S
SHORT ANSWER QUESTION
molecular spectroscopy.
I. Differentiate between atomic and of
m ? What is the wavelength range
2 What is electromagnetic spectm
visible light in it ?
and emission spectra.
3. Differentiate between absorption
4. What is a photon? nt.
5. What is Planck's hypothesis ?
Express the value of Planck's consta
?
6. What is quantum theory of light
atom ? What are its limitations ?
7. Wh~t is the Thomson's model of
scr ibe the Ru therfo rd ato mi c mo del. What was.its achievement ?
8. De
mic model.
9. State the postulates of Bohr's ato
Bohr's -atomic model?
10. What were the shortcomings of
s the nec ess ity for int rod uci ng the concept of electron spin ?
11. What wa
ple ?
12. What is Pauli's exclusion princi
is orb ita l ang ula r mo me ntu m ? What do you mean by its space
13. Wh at
quantiz.ation ? s it
m ? On which quantum number doe
14. What is spin angular momentu
de pe nd ?
? Is it quantized ?
15. What is total angular momentum
16. What is vector model of atom ?
me the qua ntu m num ber ass oci ate d with vector model of atom~
17. Na
Wh at is ma gne tic mo me nt? Ho w is it related to angular mom~ntum?
18.
19. What is Bohr Magneton ?
experiment establish ?
· 20. What did the Stem-Gerlach
21. What is LS .coupling?
cture of spectral lines ?
22.. What do you mean by fine stru
is the reason for their fine structure
?
at are D- lin es ofs od ium ? Wh at
23. Wh
Diffe ren tiat e bet we en No rm al and Anomalous Zeeman effect.
24. occur
Wh at is Ze em an eff ect ? Wh y does the normal Zeeman effect
25.
electrons ?
only in atoms with even number of
26. Define Paschen Back effect.
ESSAY TYPE QUESTIONS at ~
and emission of light by atoms. Wh
I. Explain the process of absorption
are the different types of spectra ?
~ 7
~j,
I

'
~-
102 RELATIVITY AND SPECTROS COPY

2. What is quantum theory of light ? List its achievements -and shortcoming s.

3. What were the early atomic models ? Explain- the Bohr atomic model in
detail.
4. What is vector mod~I of atom ? Explain the quantum numbers associated
f with it.
5. Explain the concepts of spatial quantization and spin of electron in
l vector atom model.
f 6. What is electron spin ? Determine a relation between the spin angular
il momentum and spin magnetic moment
7. Describe Stem-Gerla ch experiment. How does it explain the space
j quantizatio n and electron spin?
-t 8. What is fine structure ? Explain the fine structure of Sodium D-lines.
i 9. What is Zeeman effect ? Discuss the quantum mechanical theory of
anomalous Zeeman effect with suitable example.

,I 'i!
10. Explain Paschen-Ba ckeffect. What is strong field quantum number ?

PROBLE MS
·f.
i' I. A certain spectral line has wavelength of 4000 A. Calculate the frequency
and energy in e V of the photon associated with it.
[Ans. 0.75xl0 15 Hz; 3.09 eV]
2. Calculate the number of photons in 6.6 joules of energy for a radiation
of frequency 10 12 Hz. [Ans. IC>22 Hz]
3. In a particular atom, an elec.tron moves from n = 3 to the ground state
15
(n = 1), emitting a photon with frequency 5.2 x 10 Hz. What is the
difference in energy of the two levels involved in the transition?
[Ans. 21.45 eV]
4. The electron in hydrogen atom is lying in the 3d state. Calculate the

values of L, Sand J. _ [Ans. L = ✓6 tz;S= ✓3 h;J =✓15 hand ✓35 tz]

2 2 2
5. Consider an el~ctron in d512 state. Find the possible value of m1 and Jz.

; Jz =+ ~h
[Ans. m1-= ±~,± ~,±.!._ +~n +.!.ti]
2 2 2 2 ' 2 ' 2
6. A spectrome~ er can r~solve spectral lines separated by 0.03 nm. How
much magne!1c field will have to be applied to a source of 422.7 nm line,
so that the triplet observed in Normal Zeeman Effect is just resolved.
[Ans. 3.59 T]
7. A bear of elec~ons_enter_ a uniform magnetic field of flux density 1.2
Wb/m m_ the z-direction. Fmd the energy difference between the electrons
whose spms are parallel and anti-paralle l to the field.
[~ns. 1.39 x J0-4 eV]