• lf4 E)(TcHl'l "'L ncLU

.~.
·~
~ Ill·
~ o 0compon ter ents are called 0
. __tted ,n-component. -compo0
ents While the middl 131
/~.f
1S Ci"-' .
ob served perpendi
• e comnnn-t (absent . this
the light 1s
1
~
n . 1
cuartoth e I""""" m
.
,;oJJlPonents, one on either side of the original~etic
ATOM IN EXTERNAL FIELD field, three component lines are seen.
~
~·
4.1. ZEEMAN EFFECT
t ......;.,,

•-al Une. All the three components are P0bnized, o-C:,mare

. (Fig. 5.0~) .
difeetion of vtbratton of electric vector ·
(P>tariz ed perpen. di ul
c ar
-, 11,c Plllgnetic field (1t means it
to the field)
mouter compon ts .
while inn co

separated by equal distance from the

PDnents are polarizrd pcrpendicular ton-
en 15
.~ndicu lar to the magnetic
• is polarized Parallel :x'nentt he~~on ofvibra tionispa rallel
An expenm ent measunn . g the effects of th · u·on between an atom's internal magnetic. I()• ;non of a component is the same as observed Parall th
e mterac . e field). It 1s important to note
that the
moment and an external magnetic field was ..,,a:
perfonne d before ~e quantum mechani c~ theory by the r-This phenomenon oif sp1ittmg . .
of a line into three co
e1to the field
:.
Zeeman in 1896. In Zeeman's experiment an atom is placed ID an external _,,,.,1 normal zeeman effect.
m~gneti c field and its mponents (onginal absent in parallel view)
excitation spectrum is measure d and compare d with the spectrum when there /SCO-
IS no ~a~eti c field (il) AJl0018lous Zeeman Effect.
present. This could be got, for example, by measuring the wavelengths of
the radiation emitted
from a discharge tube when it is placed in a magnetic field. If the applied ma~eti c field is weak some other effects may also take part and splitting of a
When the experim ent is performe d it is found that in the presence of
siDgle line takes place mto number of components (i.e. more than three components),
the external field each such type of
spectral line splits into a number of discrete lines. The phenome non of splitting
effect is called Anomalous Z-eeman effect.
of a spectral line
into a number of component lines, with the application of a magneti c field is It is important to note that anomalous zeeman effect is generally observed while normal
called Zeeman Effect. zecman
Moreover, the observed change in frequenc y of the lines is directly proporti onal ctJect rarely occurs. So it may appear that the
to the magnitude nomencla ture is not appropriate. However , normal
of the applied magnetic field. This observat ion of extra spectral lines means that zceman effect is called normal because it can be explained from classical theory while anomalo
an atom has additional us
discrete energy levels when it is placed in an external magnetic field. The explana zeeman effect can not be explained from classical theory and that is why they are called normal and
tion of :leeman
splitting requires analysis on wave mechanical predictions which states that
both the magnitude anomalous effects.
and the direction of the orbital angular momentum are quantized.
Experimental Arrangement of Zeeman Effect 4.2. CLASSICAL THEORY OF NORMAL ZEEMAN EFFECT
Consider a source of light ray sodium flame or mercury arc placed between This theory wasy given by Lorentz on the basis of electronic
pole pieces AA of theory of matter..
a strong electromagnet. The modified light may be observed by high resolvin . .
then analysed with a nicol prism. g instruments and 'J1be centripital force required by an electron of charge e having mass m rotatmg m
a circular
In order to get a photograph, a camera is orbit of radius r is given by
2 ... (1)
used instead of the eye piece of spectrometer. F-mrw
The light can be observed both perpendicular Pole piece Pole piece where w is angular- velocity of the electron. H v is· the linear velocity of the_electron and a
and parallel to the field. To observe light parallel
to the field a hole is drilled into the pieces of
~, A ➔ • • additional force Bev is experienced by·the electron.
the magnet (Fig. 4.1.1).
Zeeman effect is classified in two categories.
(i) Normal Zeeman effect (ii) Anomalous

..:..::.:::::, "--..-..- I CI::?parallelView

to the field

perpendicular magnetic field B 18 applied, an

~ ~tion of this force is radiall~ inward
c1e.ctron 1s anticlock-wise or clock-wt~ as sho
ard
::~g.
d
4_;i.n
ding upon whether the motion
_
of
~ ~
Zeeman effect
(r) Normal Zeeman Effect i
When the magnetic field on the light is
Viewed perpendicular to the field e
observed parallel to the magnetic field, a single -l W 1 I ;;)-
line is found to split into the two components.
One component has higher frequenc y and the
.
Fig. 4.1.1
;;;:- 0
other lower frequency than the original light. (a) 0
Original light.is not observed . B=O jv
Though the original light is unpolarized, the A ~
0
CJ
(b)
two compon ents are found to Fig. 4.1.2 be ~ ,,, 2
:
r,\ (a)
polarized. In this case the outer components are : IV1 Viewed parallel to the field
bue
~ me ""'°"'
circularly polarized in opposite directions. •,
8 * Fi~ 4.2.I
- . 112
Ta ,,,1
Viewed .1 to the field
.._,,, "' this addiliooal tc,ce, ii ,io,
- of motion in dynamic equilibriUID t,ecoines
in angwar vcJocitY of Ibo ekclroD, tbon die
130
Fig. 4.1.2 F ± Bev = ,nr ((I.I+ dt»i
132
Ill .,
MODERN 'S ATOMIC AND MOLECULAR SPECTROSCOPY (B.Sc. , " ·U.K.)
... 133
r = µ, X B
Using Eq. (5.21 ). we get r = µ 1 B sin O,
mrw 2 ± Ber, = 1111w 2 + 1111i,dw )1 + 21111w dcu .
ot
.
or ± Be,, = 1111i,dw) 2 + 21111w dm
2 0 is the angle between µ 1 and B .
. db y lhe dipole when
' s
Since dw is small. so Lhe tem1 containing (dw) is neglected . ,here . I energy game
± Beu = 2111,ro dw potenba
or dw= ± -
eB [ ·: u = rroj 1f 11 ·mum potential energy) to angle
("'llll. o- o1·8 gi•ven by
2111 ~ -
11 -- 2 •
-
Pig. 4.J I
eB (} 0
or 2:rdv = ± - [·: w = 2Jrv1
2m y
m
= J rd0: µ Bf;r/2 sinOdO = -µ Blcosof
l'l/2 ·
1
1 11 /Z
or dv =± -eB-
4.m11
... (2)
y m = - µ 1 B cos 0
C ... (2)
since V : -
).
~sing Eq. ( 1), we get
eBL
dv = - ~ d). ... (3) V = - - cos0 .. .0)
l
). 2 m 2m
From Eq. (2) and (3), we have
c eB
--d). =± - - m, ·: L = Jiri+T~
). 2 4.irm
2m [t(/+T)ti ..//(/+I) [ andcos8 =
I
2 -_ eB .,I, (J + I )
). rB
or dA. = ± - · - - ... (4)
c 4;rm .
Equation (4) represents l:be change in wavelength called Zeeman shift of
l:be spectral line.
Explanation for obsena tion or two and three lines under the action or applied
magnetic = m,(;:)s
field.
gas. We can always
The vibratory motion of electrons produces emission of light in a glowing or V m = m µ .B [·: ehm = lµe (I Bohr magncroo} ]
the direction of field and 2
resolve l:be linear motion of an electron in two components one along 1 8
ol:ber perpendicuJar to l:be field. The perpendicular component is equivale
nt to opposite circular
motion perpendicular to l:be field. Now if l:be light is observed in a direction
perpendicular to the ,.!: magnetic field is applied and an electron jumps from i~tial hi_gber cncfg)' sure ff.o},
liJ
plane polarised light having er energy state (Eo)f the frequency of emitted spectral line 1s given try
field, the linear motion parallel to l:be field will send out undisturbed
frequency v called original frequenc y and l:be two circuJar motions perpend
icular to the field will
three plane polariz.ed vo = (F.o); ~(EolJ (-t { -f i) __(4 )
send two plane polarized waves having frequencies v + dv and v - dv. Hence
lines all observed and dv = - - -
eB
If in...... ... .
4.;rm -~uctic field B is applied, the total energy E of the atom ts
If l:b.e light is observed para1/el ro the field, the two polarized lines are observed
having frequen~ies So E =Eo+Vin=Eo+m,.ueB
v + dv and v - dv and l:be vibration s parallel to the field to not send any energy in this direcb01I E; = (Eo); + (m,) 1 .Ue B
hence central line having frequenc y v is missing. __,,. tt,-,e! ~ - me &equency of
11111
~- E = (Eo) + (m 1)1 .Ue B
1 1 el E·1 10 1owcr .-..... e,.;
1 "T
•,uw if l
4.3. QUANTUM THEORY OF NORMAL ZEEMAN EFFECT , ' e ectron jumps from higher energy ev
current loop and SJ)ectral line is given by _ (Eo ) (mi\ - (ni1)j l's 8
In an atom, l:b.e orbital motion of electr~n ~ d the nucleus is equivalent to a
l:be magnetic moment of the curren.t loop is given by E;-E/ - ~ - ~
... (1)
v =h- - h
µI= _ _!,_L lJa·
2m lttg F.q. (4), we get
-ve sign indicates that l:be direction _of µ 1 i s _ ~ to L. When magnetic field Bis applied to v = vo +
~
h
this dipole [Fig. 4.3.1.] then torque actmg on It 15 given by
,lfl'!l'!!'!!l1 y,?ii''l .., , .r. L , :il: •• 1
 --..-.re..',')~~❖:i! ~\.'t~0:~.-~.16' ~
134
or v =

MODERN'S ATOMIC AND MOLECULAR SPECTROSCOP Y (B.Sc. Ill

- - - - - - - - - - - - - - - - - . : . : . : . . : . , K.lJ.tq
eh
vo + l!J.m1- - B
V = Vo + l!J.m/
4nm

2mh
(-e-)B
[·.· µB
... (5) [·: Ii

== ; ; ]
==
2ni
i;]

~~ 11'1 EXTERNAL FIELD

~
vi
V2
V3 :

= VO

eB
= vo+-
eB
Vo--

----
4.nni for t.m1 :::
for 6m1 == 0

l
135
4.n-m for 6,,,1 ::: -1
From selection rules, only those transitions are allowed for which change in frequency,
m 1 = 1, 0, -1
: •Three allowed transitions are
eB
dv = ± -
v 1=vo
eB
+ 4nm
(m 1 = 1)
4.n-m
... (I)
1be frequency of spectral line having wavelength ;_ is given by
(m1 = 0) C
V2 =Vo V =-
eB A.
(m1 = 1)
v3=Vo - 4nm dv = -~dA.
W.. eB
A. ... (2)
ntmg - - = Av, we get From Eq. (1) and (2), we have
4nm
c eB
v 1 =v0+Av --dA. = ± - -
v2 =vo ;.2 4nm
v 3 =v0 -Av
A. 2 eB
Since m 1 can have (21 + 1) values i.e. a given state can split upto (21 + 1) values. But selection or d),, = ± - -- . ..(3)
rules restrict the splitting of spectral lines into three components only as shown in fig. 4.3.2. c 4nm'
where d),, is called Zeeman shift.
m,=2 Determination of elm by Zeeman Effect
m 1=1 Equation (1) can be written as ·
1=2 m,=O e = 4.n-c dA.
m,=-1 m ;.2 B
m,=- 2 e
hv0 So - can be determined by measuring Zeeman shift d,l for a particular wavelength l.
hvo- eBh hvo hv0 + eBh m
4nm 4,rm
4.5. QUANTUM THEORY OF ANOMALOUS ZEEMAN EFFECT
1=1
,, m,=1
m1=0 In order to explain anomalous Zeeman effect, we make use of concept of spin.
m,=-1 The Total magnetic momentum µ of the atom is the vector sum of orbital magnetic moment
m1= -1 Lim 1=0 Lim 1=1 1
No magnetic field
With magnetic field
;, and ,pin magnetic moment ;;, (,,. ;;; = µ, +;,) and m,gni""" of ;;; i• gi,oo by
Fig. 4.3.2. . .. (1)
4.4. ZEEMAN SHIFT µj = -µBg.[iU + 1)
For normal Zeeman effect, the spin angular momentum
= =
:.j I + s I + 0 =/
s= o, so s = o. [Fj~n magnetic field ii
is applied to this dipole
.S.I] then torque acting on it is given by ~iifJ
~
---:s
-1+ j(j+l)-/(/+ l)+s(s+l)
-+ -+ ;_J
+ l) -; = µj X B
Hence g - 2 j(j
or -r = µ .. B sin 8,
= l+ /(/ + 1)-/(/ + I) _ J .. fig. 4.5.1
+ l) - I
or g '.U(l
Also, during normal Zeeman effect Where 6 is the angle between ;jdi andle when
B·
i>oten ·
tial energy gained by the Po
-,.; ! I I Ci • ..
~ , ~
};~',) ,:
~ I, ~
u ~. ~ ~~ '("
 •.~"\, , ,, • ,·., 1'1'...
,,.~ ,·, •.,v , · - -
it .~ - ,1,;.~
tt~L~· ·•:."~:~~.-,i -,:,i- ~, ••~-- n, .,_.1~
,•.i.•~ - ~ - · -- •-~:...· , -.., , ,....,......,jf.:..,~:~
LAR SPECTROSCOPY (B.Sc. Ill K
- • .UK)
o M OUL E C : : : _ - - - - - - -~
136 MODERN'SATOMICAN . emitted due to transition of electron frorn
.ne is 137
e·s~ ~n~
f P:12 ➔ 32 S112
1
n 8=
(} = - (minimum potential energy) to angle .
1:ne IS emitted due to transition of electron frorn
2
·0 i- 2
0 0 0
)2 p312 ➔ 3 P112
Vm = J rd(}= µj .B J sin8d8 =-µj.B[cos0],r 12 m we have following value of n, I, s and j.
,r/2 ,r/2
... (2) forsodiu n l
or V =-µF B cos 8 ~vel s
j
Using Eq. (1), we g; 3
Vm = µ8 gJj( j+I) Bco s8
fS112 0
-2I -12
Vm = µB.g Jj(j+ I)B Jj(j+ I)
"'j
[.- ,os0 = ,/j Z;+I)] 32pl/2
3
-12 -12
... (3) 3
Vm = gmj . µ 8 B -2 3
or lower J2P312
If no magnetic field is applied and an electr
on jumps from initial higher state (E0\ to final 2
line is given by For D1 line
state (E0)j , the frequency of emitted spectral frequency of D line.
When no magnetic field is applied, v0 is the 1
(Eo); -(Eo )/ energy states 32s and 32p split up
vo = h When magnetic (weak) field is applied the 112 112
32s 112 will split into (2} + 1) = 2 sub-levels,
(j = ·D
Bis applied, the total energy E of the atom is
I
If magnetic field
E = E0 + Vm = E0 + g mj . µB. B j(j+ l) + s(s + 1)-1(1+ 1)
And g = 1+ lj(j+ l)
So E; = (E0); + g; (m); . µBB
and E/ = (E0)/ + gt<m)t µB B
of
level E; to lower energy level E the frequency
Now if the electron jumps from higher energy
emitted spectral line is given by
1
or g = Jil(tH~l(~)- 0
V
E; -E
1
=---
h
2(~l-m =2
= (Eo); -(Eo ) f µBB 1 1
1
+-h- [g;( mj); - Kf (mJ )f] Since so m. = - or --2
I
J= 2' 1 2
or gmj = +1 or-1
v = v0 +iiv [g;( mj); -gf (mj)J] , ... (4)
Since . 1
J =-
where
µBB =-2mh
e1iB eB · _!!_]
[··ti= 21t 2
Liv =-----
h = -4Jrm
1 l
effect is observed when the applied magnetic field is weak and tbe m. = -or --
spectral anom
The alousinto
line split fouranor more lines.
Zeem 1 2 2
Splitting of D1 and D2 Unes of SOdfum
lience
gm}= +1 or-1
2 linemishas
of DSodiu twoA.lines ""11ed D1 and D2• The "'" •ieng0, of
5890
o, lines is
5896
A and wave Jength
. split into (2j + 1) = 2 sub-levels' (1· = 2
32p11'2 Wlll !)
(!) (~) +(!) (l)-
• In spectral notation, the state of an atmn
:-.+,.;· ·
• -~- ;-:_:,. ;,.<), &:Jil/f/lint l• de111)1e(J UN (1) (2)
2S+I L
n J
And g=I+~-~
2
j (i)(1) -
 _ _ _ _ _ _ _ _:_.:.:..:_:'•• K.U.tq
I
MODERN'S ATOMIC AND MOLECULAR SPECTROSCOPY (B.Sc. Ill 139
138
~~ I <-------------r-rH------------~~::
Since j = 2, 3
1 1 1 -1
m - = - or - - Hence gm - = -3 or - 3
1 2 2 J 0 2 line I . m1=-312
According to selection rules, allowed transitions are those for which
flmj = 0, 1 or -1 except mj = 0 ➔ mi= 0 2
For !:,mi= 0
3P112 I
,--- J.. ------------- I I I I I
I -·--·--◄-- '"1=1/2
2 2
Two transitions are allowed from p112 to 5 112
For !:,mi= 1
1
1
2
1
From m . = - ... m1· = - and
2 J
1
fromm -= - - ... mJ- = --
2 2
Oiline
2
3S 112
t
:·tt'f'I ++++·H ::::·
t ~-------1- T---------r-----,------ t _-----
2
On transition is allowed from 2 P112 to S112 I I I I I
pattern for -mi=-1/2
1 1 pattern for
Fromm . =- ➔ m - =-- 01 line D21ine
1 2 1 2
For !:,mi= -1
to 2 S Fig. 4.5.2
One transition is allowed from P 112 112
1 3 2 p312 will split into (2j + 1) = 4 sub-levels (j = ½)
From mj = -
2 ➔ mj = 2
From Eq. (4), the emitted frequencies are j(j+l)+s (s+l)-l(l +l)
And g - 1+
2jU + 1)
v 1 = Vo +Av[½- (l)] 2
= v0 --Av
3
2 (½)(¾)-(½ )(¾)-(1)(2 ) _ i
v2 = vo +Av[-½- (-1)] = v0 +-Av
3
= l+ 2 (½)(!) -3
4
v3 = vo + Av[½- (-1)] = v0 +-Av
3
Since
=vo-~Av
j = 2'
V4=Vo+ Av[-½-o )]
3 1 1 3
Thus we find that D 1 line splits into four lines as shown in Fig. 4.5.2. so m - - - -- --
For D 2 1ine j - 2' 2' 2' 2
When no magnetic field is applied, v 0 is the frequency of D line. 2 2
When magnetic fied is applied, the energy states 32 p
2
and 32 5 split up gmj =
2 '3' --3' -2
312 112 'Inc allowed transitions are those for which _ o
2
3 5 112 will split into (2j + l) = 2 sub-levels (j = ½) }': l!,,,m . = 0, 1 or-1 except mj = 0 ➔ mr
or AN.
1
-== o 1
2 2
And g = l+j(j+l)+ s(s+l)-/( l+l) _ l\vo transitions are allowed from P3n to P1n 1
1
2j (j + 1) - 2
~ 1 _ .!.. andfrornmi= -2 ➔ mi = -2
l m- = - ➔ mi - 2
2•
Sincej = 1 l
so m. = - or -- }': J 2
2 2
1
-Alls-= 1
gm1 = +I or-I '
r'iVo trluisitions 2
are allowed from P3n to
25112
 EANAL FIELD
----------~M~O~D~E~RN~'~S~AT~O~M~l~C~AN~D
140 ~MO~L~E~C~U~LA~R~S~P~E~CT~R~O:S~C:O
~P~Y~(B:.S~c::_·~111, K.U.K.)
I I
- I ~ . •
-a 1·s due to preccess1o
.•field n *
n of l around H and pre . f • .
cession o .v around B, 1.e.,
141
From m. = -3 ➔ m,· = -1 and from m1• = -? ➔ mJ· =--2 ~E:::LiE;B +LiE sB
' 2 2 -
For l:lmj =-1 (Projection of I* on B) + co; (projection of s* on B)
:::: O> *
I
Two transi tions are allow ed from 2 p 2
312 to S112
* J* _h cos (L * B) + C0 • s • - h cos (s • B)
1 3 1 == O>[ 21t 5
27t
mj = -
l -- ➔ m · =--
2 ➔ mi =- 2 and from mj =
From
2 J 2
From Eq. (4), the emitt ed frequencies are == ro,• m, -+
h
21t
*
(Os ms -
h
21t
,ccording to Larm or's theorem, ... (l)
v =vo+Av[¾-(+l)] :v0 -1A v fl the precessional
angu1ar veloc1.t1es
. of
t and s' around H ~"
1 ~~
.e
* eB
v 2
= v0 + Av[-¾- (-1)] = v 0 + lAv
ro == - and ms* = 2eB
1 2m 2m
-
... (2)
Substituting these values in eqn. (5.36), we get
v3 = v0 +Av[2-(+1)] = v0 + Av eB h eB
6E =-m ,-+ 2-m5 - h
5 2m 21t 2m
v4 = v0 +Av[¾- (-1)] = v0 +-A v 21t
3 eh
6E=( m1 +2m5 ) B -
V5 = Vo + Av[-¾-<+ n] = Vo -¾Av
41tm
Dividing by he, the term shift in wave number becom
es
... (3)
0 + Av[-2 -(-1) )
v = v eB
6 = v0 -Av -6T= (m1 + 2ms) --m -I
Thus we find that D line splits into six lines 41tmC
2 as shown in Fig. 4.5.2.
4.6. PASCHEN-BACK EFFECT ON THE -.1T= (m1 +2m5 )Bm - 1 ... (4)
BASIS OF VECTOR MODEL OF
AN ATOM when L = e B/4.n m 2c is Lorentz unit.
Spin-orbit correction ; The small interaction energy due to weak spin-orbit coupli
_. In Zeem an effect, the external magnetic
field is weak by ng is given
than the intern al magn etic fields due to •
spin and orbital motion of the electron and
the coupling between 1* and s* rema ins intact
the resul tant/ . to fonn
f=-.1 T1s =at* / cos( l*/)
When the external magnetic field becom es greater,
the internal magnetic field due to spin and orbita l motion H =at* s* cos(l° B) · cos(s • B)
of the electron, the coupling between t and s
• is broken
down and both of them
precess more or less indep
are quant
enden tly
ised separ
aroun d
ately
B. This
and
is
--
l"",-
----l~--;
m
--~
--
--
s~,,
-.,,~"'
=at* cos(/ *B) •s• cos(s*B)
=amI ms
... (5)
the Paschen-ijack magnetic-field B becom ' ,.
the fine-structure splitting.
es greate r than
----------~
' /
,. -.-- ---- ) Where
R 2 2
The vector-mod el for the Pasch en-Ba ck effect is
I. li" - - - - - - -
----- m, - -
--- - - -,,
,," . .\ddin . a= n 2I ( I +a2Z(I + I) m-1 l)
shown in the fig. 4.6.1, here/ * ands* prece m ... (6)
ss about B /
/
Y or II interaction energy g;ven by eqn. (5) into eq,. (4),
independently in such a way that / the iota/ ,e,m-sruft"
/
IIYcn b g this spin b. .
(i) The projec tion of t on B is quant ised and takes ,. /
/
/
~ ~
the values m = l, l - 1, l - 2, ........ , - l. / fore- th~'+ 2m,) L + a m m,
1
(ii) The projection of s* on Bis quantised
and takes
~d
T
• T •T-( tenn-values of ,ny 1
,uo,g netd 1,vels is gh•' by
... (7)
1 Fig. 4.6.1. Vector model for the Paschen-Back here T
· ~. P4S - (m, + 2m,) L -
a m1m,. .
the values m = + - and - -1 o e term-values of the bypod,etlcal """' of g)'~~ of the fin< """" " doub~ •.(8)
2 effect in case of single-valence electron atom· L
s 2 11ie .CHEthN-BACK EFfECTOF PfUNCIPALSERfESDOUB
LEf OFSODIUM
~
Since 1115 can have two values and m1 can have
(2/ + 1) values, hence
of an atom are 2(~l + 1).- . .
Neglecting spm-orb1t mteractlon, the energy-shif
.
the possi ble no. of states
in
!~ 2lrin cipla series d bl
,... }evets to 2s ou eto f !,a(1.
"'IQ..· 1,:i"
..r . D ,nd D lioes ,f
z C separa
e., ti 1 trtJCtuf N•l i.s
uons
d,e the_,...,,
. w1·thtooutfieJd, an d strong
mm, 2p II
field
t from the unperturbed level of an atorn
3
'lll{ (us. 1/Z level. 'fhe terrns, ine s
8 tng eqn. 5.42) are given in the following table.
~-
I~ s and observed transition
T 111
143
:::::- ·p .val1eve
142 .. ues tabulate d are show~ ~chematically in the fig. (4.5.2). At the left, the field-free fine-
No field
Tenn r
MOOERN'S ATQMIC
"'1

Strong
ANDfield
ms

R SPEC ROSCOPY (B.Sc.

(Paschen
M()LECUL A -Back effect) =:::::::=;:===:
(m 1 + 2ms) am ms 1
nd es
-
, K.U.1<.)
-
0, ± I an
d 1
s are
0 shown.
~I=
I ln the strong
. . field ' the Paschen-Back levels are
A-· -
are_a so shown the figure 4.5.2. When these rules are
lead to a pattern closely resemblin
~
_,i,OIFEN
·· g a - ~ triplet.
urns - in
I -2
I
2 -a/2 -
•·I, me;ERENCE BETWEEN
BACK EFFECT ANOMALOUS ZEEMAN EFFECT AND
• CH
~
-
+ a/2 0 -21 1 0 I
Anomalous,~man effect I
Paschen-Back effect
- 1 -2I 0 -a/2 ~ s effect is observed when applied magnetic
I. field is weaker than. the int~mal magnetic field I. This effect is observed when applied
magnetic field is stronger than the
2
P112, 3/2 1 --1 0 -a/2 due to spin and orbital motion of the electron.
internal magnetic field due to spin
2
and orbital motion of the electron.
z.
The term splitting due to applied magnetic 2. The tenn splitting due to applied magnetic
(1 =I, s =½) a 0 --I -1 0 field is smaller than the fine-structure splitting
2 field is much greater than the fine-
due to spin-orb it interaction. structure splitting.
-1
I -2 a/2 3. The coupling between l* and s* remains intact ; 3. The coupling between t and s• is broken ;
2 and z* and s * precess rapidly around their and t ands* precess more or less inde-
resultant / . The precession of/ around applied
25112 0 --1 1 0 field B is relatively slow.
pendently around the applied field B.
2
4./ is quantis~d. in space such ~at 4. l* ands" are separately quantised in
(z=O,s=½) 0 0 --1 -1 0 mj=J,J -1 , ........... -J space such that m1 = I, l - 1, I - 2,
2 .............. , - l, and ms = 1/2 and - 1/2.
5. The selection rules are !:!.mi = 0 ± 1. 5. The selection rules are llm1= 0, ± 1
Strong Field and!!,. m5 = 0.
2m,.+ 2m1+ am,. m1 m1+ m. = m
~+1+1/2=+3/2 4.9. TRANSITION BETWEEN WEAK AND STRONG MAGNETIC FIELDS
a/2
No Field The number of magneti c levels into which a given state split is the same irrespectiv
W•k field /
m=312/ I I O+1/2=+ 1/2
e
strength. This number is called the "quantum-weight." In a weak field a level with a given
of the field
quanum
number j splits up into (2j + 1) levels. For a single valence-electron atom j can have only two
;arz F.
a/2
1~.....,.
~1/2
., I
a/2 F I -1+1/2=-1/2
,-- +1-112=+1/2
values
P112 I a 11 1/2
-1/2
I I 11 0-1/2=-1l 2
(1+ ½) and ( l - ½) .Therefore, the number of Zeeman levels in weak magnetic field are
---. . _g~- L JJ -1-112=-3 /2
In
(2j + l)-{2(1 + ½)+ 1} + {i(i-½l + 11=41+ 2• 2(21+ II
1/2
, *I t I* 0+112=+112 el-....a strong .magnetic field, m has (21 + 1) v ues ms
al has two values ± 1/2 (for a single valenes
which are the same as in weak field.
2
S112 *• ·-·-·'ll··-·/·-·-·-·
-----.. -1/2 . - . - . -t•-. - '41- · - .
~uun ato ) .1 split. up I1l
m . Hence, a level will · tO 2(21 + 1) 1eves,
.
1
haracterise d by the quantum
a....In a Weak magneb.c field, each of the magnetic )eve11s cumbers are m1 and m . At mtennedi .
numbers
.
j
~
6cldsj111
whiIe in a strong field the characterstic · quantum n s
ate
we may mquire
. 1 0 over to a corresponding strong-field
0-1/2=-1/ 2 J_ ' how does each weak-field Jeve g H f th various angular-m omentum vectors
□
tCVel?As
Ill : s11s 1p s11.s
h_
"""lit
111
•
ternain
a first rule the sum of the proJCC
the s ' s:

. 11·Onson o e
·
all field strengths, 1.e., m -(m1+ms
j-
) nus rule alone 1s
· hen there are more
. not suffi.
c1ent to
than one levels
Correl
\>i ate all weak ame 1or
and strong-field levels, since there are cases w
with quantulD mechanics , may be stated
Fla- 4.7.1. Paschen-Back effect of D and D lines of Na. th the . rul in accordance
1 ~ ,, same m .. The more specific
2
. l.evels withJthe same m. never em"
cross.
J
,...
144
-

· c. 111, KU
-r=========~M;O~D~E;R~N'~S~A~TO~M~~IC~A~N~D~M~O~L~E~CU~LA~R~S;P~E~C~T~RO~SC~O~PY~(B~S
. -K.)
:--

,~
~ (

11111:XTERNAL FIELD 145

lines R,, and 14 ;n electric field •bout. 14JOOo Vem- 1 , how ..,;d;recfiooa1 <lisploeement
r.,.,
know, as.,,,..,..,..., Slarl< effeet. The .

•
nal 0to the square of the
. 00
,) '[b S 1stcength.
d field "" h
. his"
Ms
ML
rlJO f the second-o, e, ta, euect m Ydcoge, Were made bYTakami.., and I<okubu ID
- - - - - - - - + 1 +1/2 , StBI'le pattem - I'
,,,,.-
MJ , , ' ~ati of H Hne ;n a field of 14lOOo ,nJt oecem, Whe""·eompo,,ent was red-shift,d by
8
,,------3 12
P312 --~f::- ------- 112 ------ ---- 0 +1/2
: , 0· . A. tion enecgy of a hydn,gen-like atom ;, an eleetrie field ;s g;ve, by
2
-- -- -1/2 e ,nteraC 3 (I l
2p,12 ---- --------3 12-::::: ===== = +11
-
+1/2 1b BF' + CF + ···········• ...
· th
~---=-==== ===='112 -1/2 r-AF+
-1/2- ..,-----
', ---- 0 -1/2
ts the shut of enecgy le,eJ, On em- 1) from the field-free state and F" e
A -
' 1 -1/2 tn
•""" AT repre:n The eo-effieients A, B and C ....... have been ealeolated from e1.,.;,a1 and
cJeC nun-mec haruca con siderations and are given by (the field is expressed in volt per cm) :
·c field stre~gtl .
quan A= 6,42 x 10- s n(nz - n1)
------ 0 +1/2 B=5·22xl 0 -16 n 4[17n2-3 (nz-n 1)-9m}+l9]
,-'
~----- --
2p,12 -25 7 {23n 2 - (n2 - n1) 2 + llm 2 + 39).
C = 1· 53 X 10 n 1
------ 0 -1/2 ...(1~
Strong Field
where n is the principal quantum number ; and n1, n2 and m1are electric quantum numbers and
No Field Weak Field satisfy the quantum condition.
m1::. n - n 2 - n 1 - 1
... (3)
Fig. 4.9.1. Transition from weak to strong field for the principal series doublet.
The !lllowed values of these quantum numbers are
2
Fig. 4 .9 . 1. Shows transition of the magnetic levels for the states S 112, P 112 and 2P312 , when
2
n = 1, 2, 3, ............ oo n 1 =0, 1,2, ....... (n-l)
magnetic field changes from weak to strong.
4.10. OBSERVED STARK EFFECT OF HYDROGEN ATOM n2 = 0, 1, 2, ........ (n - l) m1= 0, ± 1, ± 2, ...... 1 (n - l)] ... (4)
In 1913, J. Stark discovered that every line of the Bal.mer series of hydrogen atom, when placed 1Ji~ ~rst Order Stark Effect : If the Stark splitting is directly proportional to the strength F
in an electric field of the order of loS volt/cm, splits into a number of polarised components. This ad can be expressed by taking into account only the first term in eqn. (1 ), then it is called the first
splitting up of spectral lines when the source is placed in and electric filed is called "Stark-effect". Stark !!ffect. Here, spectral lines are splitted into components lying symmetrically about the
orderfie
Id-free ·· The lower states (n small) of hydrogen atom are expercted to show only a first-
It plays an important role in the theories of molecules formation from atoms, of broadening of · positions.
spectral lines of dielectric constant order Star!( effect.
The main features of the observed Stark effect in hydrogen are as follows : The Second-Order Stark Effect : If the field strengths of over la5 volt per cm., the Stark
(i) All lines of Bahner series form S)'IIlmetrical pattern, but the pattern depends markedly on the CO!npol\ents of the hydrogen lines show deviations from the shifts given by the formula for the
quantum number n of the terms involved. The number of Stark lines and the total width of the ~-order Stark effect. This effect, which is found experimentally to shift different·components to
pattern increase with n. The line Hp shows greater number of components than H a and line ; and Hy tire red or violet b y an amount propom·onal to the square of the field strength, .is called the second-
shows greater number of components than I-\, line.
th trength of
order Stark effect. In order than hydrogen like atoms, it is called the quadratic Stark effect.
(ii) The wave-number shifts are integral multip· le ofuru·t hi h. proportiona .
the electnc . the same for all hydrogen lines.
. field is w c 1s l to e s ~IFFEF .U:NGE BETWEEN ZEEMAN EFFECT ANP STARK EFFECT
. lartisation 'th . · · f£ t and the Stark effect is that each pair of
(iii) Except fur the absence of circular polarisation in Ion 'tudin
properties of Stark lines resemble th f 7 __ . gi al observation , the po ~Yels e important difference between.the Zeem~ eha: the same energy in an electric field but
. contrast, :,r components shoW
ose o L.Ct:Illan lines · But, m diij (mi and - m.) arising from a given level (j) £ thi is that the mechanism of interaction
greater separation than the a-components. • fi ld The reason or s . . f th
Cfent e . J d the machanism of mteracuon o e
(iv) The hydrogen line involving the lower ener · . hoW of the .nerg1es when in a magneuc e • .
only a symmetrical splitting, proportional to the fi lgyd Slates (n-small) such as Ha, Hp lines s..n.is cl..., . atom With electric fieid is purely electrostatic, an . an orbit of given n and lf depends .
. . ns · , .... ""-lflc di y of electron ID
e stength' about th err. field-free pos1t1o I>Ole momemen t and hence the energ . ti Id and not on the sense o rotatJ.on
is known as the first-order Stark effect of linear S tm.... .
·l'Vll. th · th electnc ie
lark effect. (c10c1. e inclination of the orbit plane w.r.t. . e rb't The states with+ mj and- mj correspond to
1
. 1ts O ·
l\W' 10
ise or anticlockw ise) of the electron
... .
)
.......~
146 MODERN'S ATOMIC AND MOLECULAR SPECTROSCOPY (':Sc. 111 , K.U.K.)
~ 147
the same inclination of the orbital plane and therefore have the same energy in a given applied 3d, 20512 NO FIELD
3d, 20312 WEAi( FIELD M,
electric field. Hence, a given level splits up into ( j + ½) or (j + 1) levels when j is half-integral or 3P. zp,
3S, 25
t 1/2 312 512
312 112 312
1/2
integral. This shows a two-fold degeneracy for Stark components. 2f'2P312 112
In a magnetic field, on the other hand, the energy depends upon the sense of rotation (clockwise
or anticlockwise) of the electron in the orbit and the energy change sign when mj changes sign.
Hence, states with + mj and -mj have different energies. Therefore, a given level splits up into (2j
+ l) levels in magnetic field. t1/2, 312
4.12. WEAK-FIELD STAK-EFFECT IN HYDROGEN
In a weak electric field, the interaction energy between total angular momentum/ of the electron
2P, 2 P
and the electric field Fis considerably less than the magnetic interaction between I* ands*, i.e., t1/2
Stark splitting is small in comparison with fine-structure splitting. In a weak electric field, the 25, 25 t1/2
spinning electron does not interact with the field because no electric-dipole moment can be induced
in tyhe electron itself. Therefore, the coupling of/ with the field is only due to the interaction of l*
CALC a
with F.
Ha
As shown in fig. 4.12.1, the resultant/ precesses around the field F with projection m where CALC.
1
mj takes values j, j - 1, j - 2, ........ - j . However, in
Fig. 4.12.2. Fine structure and weak-field Stark effect for hydrogen Ha.
contrast to 2.eeman levels, the Stark leverl + m . and-m -
1 1
. . from a particular
ansmg . leve1J·* have the same energy. l13. STRONG FIELD STARK EFFECT IN HYDROGEN
The energy levels of the hydrogen atom for the states F
Astrong electric field for hydrogen may be defined as one for which the interaction energy
with n =2 and n =3 are shown in fig 4.12.1. The field ldween the electron and the field Fis greater than the magnetic interaction between t ands*, i.e.,
free levels and theoretical pattern for Ha-line are given ,,------ Slark splitting is greater than the fine-structure splitting. In strong electric field, the coupling between
at the left and the weak-field levels and the Stark payyem "~--- mi r rands* is brojen down and t" is quantised w.r.t. the field direction Fas shown in fig. 4.12.3. While
at the right. The unpaired levels for each n (22P and ' --- lbe ~ is not acted upon by the electric field F, it interacts with the magnetic field due to orbital
32D 512 ) do not show the first order Stark splitting
312 ' '' ~on. The magnetic field due to orbital motion can be resolved into two components : one parallel
because no appreciable dipole moment is induced for ' ' bd!c field F and other normal to the field F. The precess around the component will average out to
these states. Theoretical treatment of Stark effect shows
' ' \ '¥.,.- .,., 7.a'O••As a result , s * will precess around the component of magnetic field parallel to F (or parallel
that wherever two or more levels (woth the same n and klFttself).
j but with different l) lie close to each other, the first-
In a ng electric field the first-order Stark effect is found to b_e lll:uch greater than tile secood-
stro
flder Stark ' • ·th th field F 1s given buy
order Stark effect dominates over the second-order Stark effect and the interaction energy of l wi e (5 48)
AT- ··· ·
effect. The reason why a first order Stark-effect Th -AF = 6·42 x 10-5 n(n2 - n 1) F . multi les offunctamental amount from
Ilic ~ the Stark levels of H-atom are shifted ~y mtergral
Fig. 4.12.1 Vector model for the hydrogen
dominates in 'double' levels may be explained as follows atom in a weak electric field p
: Owing to the overlapping of angular wave-function ~gmal level (neglecting spin-orbit interaction). d wn in a strong electric field, there
~ Slill gh the coupling between t,. and s• has been dbroken
l\lthou o . . Zeeman .
and the mutual energy shared by the two states, the stom this interaction energy uust as m
in either one of the shared states will possess a net tflect) ~ W~ak magnetic interaction between them an
ekctric moment. 18 given by
The selection rules for the weak-field Stark effect are th
e same as those for the Zeeman effect : T =a1* scos(l•s)
•
drnj=O± 1
= al*s* cos (l*F)· cos (s*F) .. (2)
The levels with /im1. = 0 are are called .71'-com
a-components. · ponents and those worth din . = ± I give = al* cos (I *F) · s* cos (s*F)
J
... (3)
"'llllg
t\ri.1:_ a m1(2),
eq~ (I) and-- eqn. m5 each ,"""8-6eld ienn-stuft is gi,en by
T + T = 6•42 x 10-5 n(nz - n1) F + am1 "'s
148 MODERN'S ATOMIC AND MOLECULAR SPECTROSCOPY (B.Sc. Ill, K.U.K.)
149
The following tables gives the values of relevant quantities of eqn. (3) for the ~ust three state~
am, m, m,+m.+m,
= I, 2, and 3) of hydrogen atom. The m values have been calculated by usmg the quanturn- n(llz-n,)=+6 "c)-0±112. ±1/2
condition ml = n _ n _ n _ 1. The coeffi~ient in the last column are not all equation and is the n-2
2 1 n---3
measure of spin-orbit interacion. From the above table, it is clear that Stark shift for the groun<J.
state (n = 1) for hydrogen atom is zero. am1 m, m,+ms+m
1 +3+a/2-a/2
n(n2-n,)=+2 0±1/2=±1/2 +1+112=+ 3/2
-1-1/2=-3/2
+1-1 /2=+1/2
TABLE-ENERGY FACTORS FOR THE STARK EFFECT IN HYDROGEN + 1+1/2-312
~
-·
-=<:
0 -1 /2=--3/2· -1+1/2=+5/2
+1-1/2=+1/2 ~ +a- -1-1/2=-5/2
:::: 0+1 /2=+1/2
n n2 n1 n2 - n1 n(n 2 - n 1) m1 ms am1ms -1+1/2=--1/2 -c--! +2-1/2=+3/2
1 0 0 -+-
1
,., 0
- 0±1/2=±112 -2+1/2=-312
+1

0
+1

0
0

0
0 -1
1
+-

-
± a/2

No field Weak field

Strong lleld .:-a[~ +2+112=+3/2
+a3/2 -2-112=-3/2
+2-112=+3/2
-1+1/2=-112
-?
1
~ O 0±1/2:±1/2
Strong field
2 +1 0 +1 +2 0 -+-
,, 0
Fig. 4.13.1. Stark levels for n = 2 and n = 3 levels of hydrogen in weak and strong field.
1
0 +I -1 -2 0 ±- 0 Toe selection rules for a strong electric field are as follows :
2
1 !lm1=0, ± 1
0 0 0 0 +1 ±- ± a/2 /l.m5 = 0
2
+2 +2 0 0 -2 ±.!. ±a n("2-n,) 11:
I
(J
I
2
1
3 +2 +1 +1 +3 -1 ±- ± a/2
2 n=3
+2 0 +2 +6 0 ±.!. 0
2
+1 +2 - 1 -3 -1 ±.!. ± a/2
Ha
2
+1 +1 0 0 0 ±.!. 0
2
n=2-
+1 0 +1 +3 +1 ±.!. 2
± a/2
2
0 +2 -2 -6 0 ±I
2 0 n·I 11-1: 11 l e (1 II I I I 11 a
0 +1 -1 -3 . Using th Fig. 4.13.2. Strong field strut effuctofH,-line.
+1 ±.!. + a/2
2 ...,,, ~n, is giv . ction roles, the str0ng-field strut pattern ofHoline· neglecting spin-o,b'I
~ ese sele ·
0 0 0 0 +2 ±.!. ±a
I I •lion in ~; m fig:4. 13.2. This p•- is found wbdngood ,greemeot wilh the expoim<n.:i
2
•·.4. HYp relative shifts and intensities.
- 1.iany ERRNE STRUCTURE Of SPECTRAL LINES
2
""'1..,
~
The Stark-levels corresponding to the weak and strong ~ld for n = 2 and n = 3 are given below: bi
<t,-1 ~yfine-structure-componen• of spectral·'"'"''· wheP ex- · ed "'·th·
. "''"""""" ba-'ng
11t,,...( - Q.resolution, are turt1ter splin,d into con>P""'"" w,lh seP"'"°." of the rude, of
...., and . ) which is much s,oaJler Iha! mose of ,n,Uq>lcl sirucwre- TM ,s c,1100 bypafin<-
4
1s caused by the properties of the atoroic nucleus.
.-
E)(TERNAL FIELD
.-.1N . . .
~~
•• ,,.., • -~• cot"I n AR SPECTROSCOPY (B.Sc. 111 KU
MOOERN°S ATOMIC N'I"' ~ - - . .tq
sel O• ± 1 (but O ~ 0)
150 ' ·
ection rule for F for electric-d1po1e transition arc :
.....~ source oflighl musl be one givino..__v
151
r- _ _ 'JbC/}F=
the ~-q>cnmenral srudv of h\"perfine srructure- u""' • . - "' ery
~
I"1l
sharp line such _ · unnnier-Gehrcke pla1e. echelon graung. laser, et
as ~-}>ero( spec~ h·_,.rfine structure: The first is due c. . be ➔ ➔
..- interaction tween J and I (simiI .
There are two t)p:=s of nuclear dfecis that produce Jl"-'W . to the •.,..., ar to spin rt· •
...:""--- - - • ( - 'led ,s·oro,µ,·c el1'..rf). The energy levels of 1soto~•
presa:.ce of Ulllocnt 1sorop1c species c.u · 'JJ"· • . - . . ,...""' ~ be -o 11 interaction energy) can be proved to
slightly displaced relatiYe to each other, producing spectral lines havmg Slightly d.iffe~nt wave
numbers.. This is beause Rydberg-constant depends upon reduced mass of the atom and increases
E= ½A' [F(F +l) -1(1 + l) - J(J + I)]
'11,;th incrcasie in mass of the nucleus and attains a nearly constant values for heavy nuclei. The 1be separation between successive hYJ>erfine tru ... (5)
variation in Rydberg-constant is particularly marked in hydrogen. Each of the first four membe~ t (F + 1) and then F in the eqn. (5) and then ~ cture (hJ_s) levels can be obtained by substitutinf
of Balmer series H . H ~ and H bas a weak component on a short wavelength side separated b firS ng the d1fferenece, i.e.,
1-79 A.• 1-33 A. 1-19C A.• -pimd 1-12OA• respectively. These swn"
-L'A.- "th th
agree~ . eoret:I
'cal al
v ues if these
y
short-wave.length components are assumed to be due to presence of an isotope of mass 2 (deuterium).
i1E;,½A' [(F + 1) (F + 2)- F(F+ l)=A'(F + l)] ... ( )
6
( F=5 =9/
1 2
Many cases of iso{ope-shift are not as simple as that for hydrogen. In fact, for rare-earth and 1bus the energy interval between successive hfs level is
bea,..;er atoms. the main conaibution to isotope shift is not due to difference in mass but due 1
_poporrlonal to the larger of the F values (Lande's interval 4
change in nuclear radius with mass and deviation of nuclear-filed from being purely Coulombiano
The second type of effect arises because the nucleus possesses an intrinsic angular momen~ rule)- Toe order of hfs levels in some hYJ)erfine multiplet is
(N~lau spi,,) and the associated magnetic moment. An interaction between this magnetic moment .,nna1 (smaller F-level deepest) while in others it is inverted
~ mtcmal magnetic field produced by swrounding electrons causes hyperfine structure of spectra] (]argeSt F-level deepest)
lines. As nuclear magnetic moment are smaller than electronic magnetic moment by a factore of As an example, let us consider the hyperfine structure of 3
4
bismuth line A = 4722 A. For bismuth, I= 9/2. With nuclear 5
(IS~), the hyperfine shifting is smaller than the fine-structure splitting caused by spin-orbit 1
u
interaction of valence electron (s).
spin I = 9/2 and J =
2 , the initial state is split into two hfs II I I I
The intrinsic angular momentum of nucleus
given by
➔ ~h •h

I and the associated magnetic moment µ 1 are

➔ levels with F = 5 and 4, which are in normal order. The final
slate with I = 9/2 and J = 3/2 is split into four hfs levels with
F = 6, 5, 4, 3 which are in inverted order.
rv!\
Bismuth A4722
lll=v~(l+l) - = I - ... (1) The selection rules allows six transitions. Hence A= 4722 J1I&. 4.14.1. hfs of A = 4722
21t 21t A line of bismuth.
Aline of bismuth consists of six hfs levels.
➔
µI =g1 ( e
2mp
) ➔I, ... (2) 3
Example 4.1 : Calculate Lande's g-factor and total magnetic rrwmentfor the term F711•
where g1 is called nuclear g-factor. The magnitude of this magnetic moment is given by Solution : For the doublet 2p712 state, l = 3, s =1/2,j =7/2
The Lande's g-factor is given by
e ) ~ h • eh •
µ1=81 ( - yl(l+l)-=g1I --=g1I µN, ...(3)
2mp 21t 41tmp ✓i~U__+..:1::....)+_s~(s__+_l~)_-~I(I_+_l)
g=l+-
2jU+ 1)
where µN = ~ = 0 -505 x 10-
26
rr- 1 is called nuclear-magneton.
4Nnp
7 9 1 3
Vec:tor model of an atom with nuclear spin : The total ---+---- 3 · 4 142
angular momentum F of the whole atom is sum of resultant F" =1+22 22 -
7 9 126
angular momentum ~ for the extra-nuclear electrons and "" ' \ 2----
" 2 2
the nuclear spin angular momentum I*, where F can have
"" ' '..... __ _
The magnetic moment of the atom is given by
1· <-~~~~
values - \.-I
F = 1 + L 1 + I- l, ..... I 1 - I I ...(4)
Due to interaction of 1* .and I*, both of them precess
\
\ , __ _ ,.- \ I
I \ .•
--+r-..1
h .• h _:.!'_
µ=g·-2m-·J -27t =g· 4nm
.g;;»
--x
around their resultant Fas shown in the fig. (4.15.I). The ~-\--
precession of 1• and I* about F is much slower than the ' '
', ' =g-.Jj(j+l)µB
precession of L* ands• around~- Due to this interaction, a ','
particular i.ne-structure level splits up into (2J + l) components = 142 X {63 X 0-928 X 10-23 JT-1
(if 1 s Oand into (21 + l) components (if I s J). Fig. 4.14.1. Vector model of an alOJll
taking into account nuclear spin
126 f4 1
= 4·3 X 10-23 J'I
 -- - · - - . .._ . . . . .. .. -- . ,' \ '\ ~ ... . . -
I"- ~'?", ~j
I ~
••• '" a ., • ,: ~ -
RNAL FIELD
152 MODEAN'S ATOMIC AND MOLECULAR SPECT
ROSCOPY (B.Sc. Ill, K.U.1q ~
~ 0- 2 x14
10 om
2 • ..,(40283 X
·. ,.. 153
sive 'Zeeman-levels for P3/2 term in-: ;;
Example 4.2: Calculate separation between succes ::::O· 3 A.
magnetic field. 28
44
Solution : The g-factor for 2p3/2 term (1 =I ' s = _!_2 ,j = 2)
2
is given by < 0-0
P--- ,idus et• Calcu
e late the umde•, g-facto, Jo, th, 3PI t,n,, of the 2p.
3, config,mno, ofthe
atom i, placed in o,, ext<mal
tesla.t to e,a/u ,e the spUtnng of the b,L when
4IO"' a le ·Oif·O·h l ,esul
'.i-rnp
icjieldFor 3p I -leve l (L = 1, S = 1, I= 1), the g-facto, i, give,
bJ
~ - ~ +Ll -1-2 4
,ti{:-:, tiOD,
~,1,,,J
g = 1 + j(j + 1) + s(s +I) - /(/ + 1) = + 2 2 2 2 3
SOi8 l) + S(S~~ - L(L + 1) =-
+ 1)~
2j(j+ l) 2.l .~ 3 J(J+ ....:...._ - -
2
g :::1-1 2J(J + 1)
2 2
The separation between Zeeman levels from the hence the term 3p splits into three components
(lor J::: l , th~ possi ble value s of MJ are 1, 0, -1,
field free position in weak magnetic field is given H tting given by 1
by .!11.spti L -1
..
- ~T = mjg L m-1,
where L = ~ = (46 -7B) m-1

.. . (1) mg=6/3
4/3 mga:l/2r:i~,-\ ""' -11 T = Mrg· m
wbefe- /1T is the shift from the field-free position
eB 3p ,. _,.
· n by -47t~ -- (46-7B)m- 1
2/3
41tmc 1/2 . Lopre nts-um·t, give
~L~ 1-----:~',,
P31~::··· ···4/3·········=;~~~ )
2
is called Loren tz-un it , _ _ _.&..0.07crr
___ r1_
2
For P312 term, there are four magnetic levels i
corresponding to mj = 312, 1/2, - 1/2, 3/2 shifted
from the field-free-level by mj g = 6/3, 2/3, - 2/3,
4/3 t \.. / :
-312 ········: :::\. /
- 6 / 3 - - - - - ---- ...,::::::::. ..,, ./

- !!,,.
=±7 m-1

T= ±
2
X 46 · 7 X 0-1 m -I
Fig. 4.4.1
and - 6/3 (in Loren tz unit). A graph ical '••······..•·-··· s
). Hence the level corre spond ing to M . = O remain
representation of this splitting is shown in fig. (4.2.1
1lllShifted and the other two levels are shlfted by 7 m-1
From the fig (4.2.1), it is clear that 2P312 term splits Fig. 4.2.1. Schematic orientation diagra m of an
2 n from the field-free positi on, as show n in the fig. 4.4.1.
atom in a P312 state showing the resultant Zeema
4 of strength 0-1 Wblm 2. Calcualate the
up into four equispaced levels with separation levels in a weak magnetic field. Example 4.5 : As atom is placed in a magnetic field
3 l = 3 in an atom, the magnetic moment of
times Lorents unit. precessional frequ ency and torque on an element with (M.D. U. 1997)
tltctron makes angle of 45° with magnetic field.
Example 4.3 : A sample of a certain element is
placed in a magnetic field of 0-3 Wbm - 2. How magnetic field is given by Larmor-
Solution. (i) The prece ssion al frequency of electron-orbit
wavelength 4500A, considering norm al 7Leman
for are the 7Leman components ofa spectral line of 1heorem:
(K.U. 1997 S)
effect.
the components of a normal Zeem an triplet is eB
given by ion. The wave number separation between
Solut COL =-
2m
,.,-
uV= --meB -I
where e = l -6 x 10-19 C
41tm
m = 9-1 x 10-31 kg
_ l-6xl Q-l 9 xQ.3 B = 0.2 Wb m-2
dv= --- --- ~-: --- -7
3
4 X 3· 14 X 9 -1 X 10- ! X 3 X 90 8
l-6x 10- 19 x0-2
= 14 m- 1 COL 31
2 X 9 · 1 Xl0-
we know that, v1. .= I
9 1
v•M +A ·dv=O ("~ = 17-6 x 10 rad r
11
The torqu e on the electr on-or bit is given by
IMI= A·_6v
V
➔ ➔ ➔
ln 't =µIX B
= 1.2 -6v Illagiu tude,
(·:v=±) 't = µI B sin 8 = [z{z + 1) -~-
41WI
B sin 0
154 R SPECTROSCOPY (B ·Sc. Ill, K.U.tq
MODERN'S ATOMIC AND MOLECULA 3 => J = 3 ( I F -term) - - - -
n L.= ~
..,
~A_
3
150
Ju. x l-6x 10- 19
x 6 -62x 10-34 x-2x sin 45°
31
J ·~ sn~~!!;Zeeman
t allowed).effect takes place for the lransitions 10, _ lp W>d 1F, _ 10, (tran.itio,,
4 X 3 · 14 X 9 · l X 10- %..::.-1=
Ip isno ---------
1
---.-------
= 4-546 x 10-24 Nm
. · 2D312
E xamp Ie 4.6 : Compute ?.eeman components for the transition ➔ 2p3/2· ,,. M.
-
,,. -
. . (M.D.U. 1998)
1D
2 --~~--.... --
,2
1
Solution. It 1s a doublet-doublet transition so the Zeeman _pattern would be anomalous. The ',' .... I
Zeeman levels, g-factors, g-factors, Zeeman shift (in Lorents urut) for the terms 20 312 and 2p ' 1
given below : 3/2 are 2
Term
No. of Zeeman levels
(2j + l) g
-
mi m/g
203/2 4 4/5
3 l
±- ±- ±~ ±~
-
2' 2 5' 5
1p
,, --- '
r
,, r f ♦
2 3 l .......... r
-
1
P3/2 4 4/3 ±- ±- ±~ ±~
2' 2 5' 3
The splitting of these terms and Zeeman pattern is given below :
Using selection rules /im , = 0, ± I, Six a-lines and four .7t'-lines are obtained.
ml
+3/2

NO Field
.1.- a a
Fled
-.=::-
20312--------:.::: +1/2 Fig. 4.7.1
1/2
3/2
,,
"'-
+3
,, ,, +2
,, ,,, ,,
~~~---
-~--""( --- --
,-- 0
+1
•~~~. :,-
1 ,-- -1
F3 I . -2
' ', --3
-::- --
+3/2
2p3/2 ,-:_·<: +1/2
, 1/2
~2
a ,r a
,
l 11 1111 11 I ,,, ,, ~
-
~
+2
+1
-0
Fig. 4.6.I 1
D2
.,, .. ~-:.,,
('c=--- --
--- ·- -- -2-1
Example 4.7: Show normal ?.eeman effect for transitions arising out of p-d system. A) --- -
...........
- . IX
-
(K.U. 1990o
=
Solution: For p-electron, l 1 I, s 1 l =2 Ford-electron, 1
Using LS-coupling scheme, the possible values of Sand Lare: 2
=2, s2 = I
2
J_ ~
S = 0, I (singlet, triplet) No Field
L = I, 2, 3 (P, 0, F-states)
Normal Zeeman-effect takes place only for singlet (S = O) states. ll>atn 11r,~7J
For singlet terms, we have '""crro pie 4JI. What magnenc flux ,i,,,sllY 8 ;s ,,,pnred" ,;,,,<" 1M ,.,,,..1 :,,,man effect if
S =0, L = l => J = l ( 1P 1 - term)
S =0, L = 2 => J = 2 ( 1D 1-term) s.i.,.;:rer can resolve specrrol """ ,eparated by MA oJ 5,XX, A?
n. We know that
-~
156 MODERN'S ATOMIC AND MOLECULAR SPECTROSCOPY (B.Sc. Ill 1d011• 157
- - - - - - - - - - - ~ · • K.U.1<.)
dJiS cas;·o--9m, dJ.. = 0-0116 m= 0-011 x lQ-9 m, B:: 1-00 T
ldll ldEI = (;;)B SOO )(the relation
ebave 4nc
A. he he elm = - 2 -·d,l
A. A. ;_ B
_~(~)(2m)
B - lJ l eh
. the various values, we get
f11ttUlg
elm= 4nx3x10sxO •Oll6x10-9
3
-(0·5A)(l2·4 Xl0 eV.A) (500 X 10- 9)2 X 1·00
- 5000 A 5000 A
= 1·758 x 1011 C/kg
1 ) -HST £J8111Ple 4.12. A sample of certain elements is placed in magnetic field of flux density 0-3 r.
( 5·79 X 10- 5 eVff -
Example 4.9. A spectral line of wavelength 4500 A when produced in a magnetic field of JO 81119 fiar apart are m -- J-7588 x Ja1 I Cl
the Zeeman components of wavelength 4500 A·? (Given !....
tesla is found to be a normal aeman triplet. Calculate the wavelength separation for the various
components of the triplet.
kt}Solution. The separation between adjacent components of a nonnal Zeeman splitting is given
Solution. Change in wavelength of the Zeeman components is given by
by
d),_ =
J
±-;
2
(_e)B
4irm
dv =~=!....
4nm m 4,r
B
Putting the various values, we get 11
0·3T
= 1-7588 x 10 C/kg x 4 X3 ·142
10
(4500x10- )2 ( 1·6xl0- 19 )
d),_ = ± · X - - - - - ~ X 10
3Xl08 4;rX9·1Xl0- 31 - 5·2764 X 1011Hz
- 12·56
= .± 94.3 x 10-12 m =0-943 A Also, we have
So Zeeman triplet has wavelengths
;_2
A. I = 4500 - 0.943 = 4499·053 A dJ.. = -dv
l 3 = 4500 + o.943 = 4500•943 A C
11
Exainple 4,10. A spectrometer cqn resolve spectrql lines separated by 0-03 nm. How much (4500 X 10-!0)2 X 5·2764 X 10
magnetic fie/4 will have to be appij_ed to a source of 422-7 nm line, so that in the Normal' Zeeman or d}., = - - -3X 108 X 12·56
effect in triplet-is ju.st resoived? (Given elm= 1-76 x JOll Clkg)
Solution.
We have the separation of triplet given by Exam
"Paratel pl: 4.13. In_ a nonnal
= 0-0283 A experiment, the cak;,,m 4226 A Un, ,plit, inJo 3 i;,,,,
z,,-
A.2 e Soiuti Y O-Z5 A in a magneric field of3T. Fmd elm fo' the e/,cm,n from the" - .
d),_ = + -· --· B
C 4Jlm on. We have the relation
B = dl 4;rc
J2 · elm
d).
-
id El
=- == ~
(;;)a
In this case ).2 ch en
9
l = 422-7 x 10- m, d), = 0-03 x 10-9 m, elm= 1-97 x 10 11 C/kg
0 · 03 X 10- 9 X 4;r X 3 X 108
d).
-
(~}B
= =C ~
· B = 2 g -3•6 T ).
·. (422 • 7) X 10~ 1 X l ·76x 10" I ,t
Example 4.11. Calculate elm for electron from the Zeeman separation 0-01 J6 nm for a spectra
line 500 nm in the presence of a magnetic fled of 1.00 tesla.
i'
158
--------- ------...: _=·•
MODERN'$ ATOMIC AND MOLECULAR SPECTROSCOPY (B.Sc II
I, K.U.I(.) I)~"'
. ,,;sion that the outermost orb·t
. ..ro•~
iii . ro0teonost orbit, which are full
i can ha
. ve am~,,:- 159
~ 4;rr C pr, contain -----unurn of 8
=-·-•d). ,..A in the outermost orbit is even th an even nurnbe f electrons. Thus all orb"ts
m B ;._2 r.~ nl b . ' e tota1
, , - :I.Sc satisfied o Y Y singlet states Whi h .
r o electro un.
number of el
,
~s. "nen the number
4;rr 3X 108 -I ectrons IS
~
C ID h,- .
= - X ms x 0-25 x 10- 10 m of electrons.
'
""" 1s possible 0nl . even. Now s = 0
3T (4226 X IO-I0)2 ~r Ytncas Of ·
1~ ,. ...n.;ch of the elements H He L' M e atoms having
n_.,,. ".... ' ' i, gandN
w ? a might exhibl't DOnna} 7.eeDJan effl
= 1·76 x 1011 C kg-1 [ ·: 1 T = 1kg2 == ~] ,jtS1 . .
ect
A.s C.s ,; Electromc configrations of given ele
_, H 1 ments are •
~ . ";.;~ ..1:08JEOIVE iYPE·~-- .-
= ls 'He== ls2, Li= ls2 2 , .
Mg = 1s2, 2s2, 2p6 3s2 and N~ ~ is2 2 6
-- ~ ~~ ~~ ~~~ :;;:;,; ~~
}lel'C oolY He and Mg have even number of el - , 2s , 2p 3s1.
~~>~~ Li and Na do not exhibit normal Zeeman ~trons, so they exhibit nonnal Zeeman effiect,
.¥ , ~, - ·~ _ , _
~ JI, Ii . euect.
1. In normal Zeeman effect, a level of given l splits into : Q. 3, Give an app cati?n ~f Zeeman effect.
,._. An important application of zeeman effect · th .
(a) / levels (b) 2/ levels is e expenmental determination of elm
(c) (21- 1) levels (d) (2/ + 1) levels. 4nc ·
e/m = - 2-Af
2. In normal Zeeman effect, a spectral line gets split into : Jle,e A. B
(a) Two components (b) Three components
Hence c/m. can be calculated by measuring the zeeman shift Af £ .
(c) Four components (d) None of above. · fi eId B 1s
· appli ed . or a given wavelength ,t ,
,hell amagnetic
3. In anomalous Zeeman effect, a spectral line gets split into : Q. 4. De6?e n~rmal zeeman effect. What is the difference between transverse zeeman
(a) Two components (b) Three components 11kt md longitudinal zeeman effect?
(c) More than three components (d) None of above. Ans, The splitting of a spectral line into three components under the effect of a magnetic field
4. In Zeeman effect, when the external magnetic field is weaker than the internal magnetic il tmwn as normal zeeman effect.
fields due to spin and orbital motion of electron then coupling between I* and s* : It is observed that when normal Zeeman effect is viewed in direction perpendicular to the
(a) Remains intact (b) Broken h:tion of the magnetic field, all the three components can be seen. This is called transverse
(c) Could not say anything about coupling (d) None of above. aan effect But only two outer components can be seen when normal zeeman effect is viewed in
5. Anomalous Zeeman effect is observed when: adirection parallel to the magnetic field i.e. central line is missing. This called longitudinal zeeman
(a) Applied magnetic field is weaker than internal magnetic field effect.
(b) Applied megnetic field is stronger than the internal magnetic field Q. 5. State Paschen back effect. f ·
(c) Does not depend on magnetic field Ans. Paschen Back effect states that whatever be the anomalous zeeman pattern ~ given °
. . al ximates the normal zeeman tnplet as
(d) None of above. --.i line m a weak magnetic field, the pattern ways apP_CO talc either due to the
I
~ ,field strength is progressively increased. This red~c~on may e Pace
~nee of lines or due to the disappearance of certalll lines.
l ANSWERS]
Q, 6. Why anomalous zeeman effect is called so ?. ld not ~ explained on the basis of
I. (d) , -- I . ffi t, because 1t cou
2. (b)
3. (c) 1U1Bo t ts called anomalous zeeman e ec
4. (a) 5. (a). and~ beman effect.
claaaicaJ. pby~ics.
Q, 7. Name some sources of elements for normal f 1ements like Ca, Cu, Zn, Cd etc. and
. ed from sources o e
~<Le =•~=
Ans.
~!
ts like Na, Cr etc. ed . magnetic
. ;,t ~ ~ ~ b &
a
Normal zeeman effect is obtain
OUs zeeman pattern is obtained from eleme:e )engtb 4226A when ome:e =~nted
by
f
-1 . .
ifl"'[ll . 8, A certain transition is an ·at001, of ff tt rn whose components
Q. 1. Explain why normal Zeeman effect occurs in atoms with even number of
or Zee an pa e
5':ic 101 Tesla exhibits a normal ;: vaJue of elm. . nee for nonnal Zeeman pattern
die ·-'-- cycles per second. CaI~te dB the frequency differe
Ans. Nonna] Zeeman effect occurs only 10 atoms which have a total spin S = 0, so that ia: "'Ill. When placed in a magneuc fiel '
spin magnetic moment of the atom is zero. For S to be zero, the number of electrons in the .:>utennoSl
2 shoold be even. The number of elec1rons in lhe nib Olbil can have a maximum value
valence 011,il
= e ) eB
2
=
equal 1o 2n i.e. lhe firs1 orl>i1 can have 2 x 1 2 electron,, SCcond 2 x 2' 8 electrons and so OIi !iv = (-4,n,n a==--
"'4,r
 • '\. . . . -
~1 • .,. ~EAN AL FIELD
·~
160 MODERN'S ATOMIC AND MOLECULAR SPECT
~.: ..-- --- -- - -
ROSCOPY (B.Sc. 111, K.U.K.) t1,cp1a in Pasch en-Ba ck effect in th . .
P'"
e Pnnc1pal
series doubt 161
e = _ _
4.7t~V 4X3 . 142X 5.6XIO IO .. That is Pasch en-Ba ck effect ? Ex . . ct of f'th'
1
or
".. P1ain trans· t' 1um atom.
m B 4 l11 what way norm a1 Zeem an ·effect antl . 1 ion from weak to . . u. 1996, K.U. 1996 A)
(MD
= 1.759 X 10 11 C/kg Paschcn-Back effect stro~g magnetic field levels.
Q. 9. If ~v is the frequency shift in the Zeeman d"ff are different..,
splitting of a spectrum, determine the Write down 1 erenc e betwe en ano
relationship to give corresponding wavel ength shift ma 1
ous Zeeman ell <M.D.U · . 2001
~- 2007)
Ans. The freque ncy shift in Zeem an spectrum is given ect antl Paschen-Back eff~L
by
1u,~ ShoW Pasch en- B ack pattern schemafica11 Yfor a p · ·
nnc1ple series doublet 0 f . . U. 2006 S)
electron atom. (T<
_e_B a: ? a smgle valence
~v = 4.1tm .i ll What is stark euect
P• . . Expla in the strong fi
rules used m it.
. te Id stark effect . h (MD . . u. 2002)
m ydrogen. Mention the selection
c d). 2 tS. What is Stark effec t? Expla in weak field Stark
As v = -;dv =-c -ord ).=-).-dv .
effect m hydrogen atom. (M.D.U. 2003)
). ;_2 C
or ;_2 e
19, Distinguish betwe en weak and strong field Stark effect
on the Ha-li ne of Balm er series.
6M.~. 2
U. 002, K. U. 98, S 2002)
th
~l = d). =+ - - - B . . hb (l · escnbe e effect of strong field
4.7tm It Distm gms st part M.D U 2006) (KU 1998A)
~
C etwee n Zeem an effect and Stark effect. · · · ·
11, What is strong field Star~ effect ? Derive an expression for
~T (shift of each term .
· presen
· ce of strong electn c field.
QUESTIONS ... h rfi
.p. p1scuss ype me structure of spectral lines. (M ) m the
.D.U. 1998)
(M.D.U. 1998)
1. Expla in norma l Zeem an effect using classi cal U, What factor s are respon sible for hyperfine structu re of a spectra
idea. Show norma l Zeem an effect for l line ?
transi tions arisin g out of a p-d system. (M.D. U. 2000, 2002)
(K. U. 1998, A) 14. Show diagra matic ally the splitting of D-lines of sodium
Or as a result of anoma lous Zeeman
Give the theory of norma l Zeem an effect and derive ~fleet.
an expre ssion for freque ncy shift (K. U. 2002)
produ ced by magne tic field.
(M.D.U. 2007)
25. Expla in how differ ent factor s are respon sible for hyperli ne structure of spectral lines.
2. Distin guish betwe en norma l and anomalous Zeem (M.D.U. 2003)
an effect.
(M.D.U. 1997, 98, K.U. 98 A, 2002) 26. What is norm al Zeem an effect ? Explain it with necessary theory
3. (a) Deriv e an expre ssion for magnetic interaction energy and derive expression for
of single valenc e electr on system. •
(M.D. U. 1998) ·;?._
Zeem an shift.
Why does norm al Zeem an effect occurs only in atoms
.
with an ~ven number ~f electronS ?.
(b) Expla in anoma lous Zeem an Effect . 'Ill .
h lines of sodium on the basts of Zeema
4. Show norma l splitting in case of transitions betwe (K. U. 2002) "°'Descn be the specia l patterns expected fort eyeIIow b
en singlet terms 1 p 1
5. Comp ute Zeem an compo nents for the transition 2 1 - D2 .
D ➔ 2p .
312 (M.D.U. 1994, 98) f9 De effect.
. .
nve an expre ssion for the splittin Of I Is in a normal Zeeman effect.
6. In what way normal and anoma lous 312 ,• .
Zeem an
atom- model , derive an expres sion for frequency-sh
effect s are different ? On the basis of vector I g
tt' What is Zeem an effect ? Under what con&. • 0 ~
eve b . the anomalous Z,eeman pattern ?
ift ~v produ ced by magne tic field in ;, Wb tton f gnetic field on energy levels of an
case of norma l Zeem an effect. 1• at is norm al Zeem an effect ? ExpIam · the effect o ma
pectral Jine splits into three spec tral
7. Distinguish betwe en normal and anomolous Zeem an Show that a s
effect. Derive an expre ssion for change atom on the basis of quantu m th eory .
produ ced in the energy of the electron of the atom .& lines in norm al Zeem an effect.
under the effect of a weak magnetic al s ieeman effect with special reference to
field. o1 o·
8. (M.D. U. 2004) 1scuss quant um mecba ruca . 1th ry of anom ou
Deriv e an expression for lande's g-factor. Now eo .
will you explai n anoma lous Zeem an effect D1 and D2 lines of sodium. Draw clear &agr runs al . d anomalous Zeeman effect. Denve an
.
of sodium yellow lines with its help ?
9. Deriv e expre ssion for Lande
(M.D. U. 2000) 33 U.TL o·"
' "uat is Zeem an effect ? iuerentiate norm an
's g-fact or and explai n with diagrams the anoma lous Zeem an tum theOf')'• d derive the expression
e
10.
patter n of D 1(5890° A) and D (5896 A) lines of
Distin guish betwe en norma
2 sodium. ¾4 Xpression for Zeem an sbi
•ft sing quan
u
nrv theOr)' an
1 . it with necess... ,
l, anoma lous Zeema n effect s and Pasch en-Ba ck effect. Find the • What is norm al Zeem an effect ? EXP ron , zeeman effect with special
expre ssion for energ y shift in Paschen-Back effect
for one valence electr on atom. 3 fot Zeem an shift. . al the of')' of ~on1a l;~ a nect diagram
S, Dis~uss the gener al quantum mech:~cD2lines o_fsodi~ ~ calculate the value illustrate
to
11. State and expal ain Pasch en-Ba ck effect using vector (K.U. 1998) of normal
atom model . tefere nc eto Zeem an pattern for D~? lines of sodium -
(K.U. 1996)
the Zeem an splitti ng of Dt and •1h
Zeem an shift in terms of w a v e l e n ~