CHAPTER I

ATOMIC STRUCTURE

Bohr Atom Model

Rutherford's nuclear atom model led to certain consequences which were in contra-
diction to the experimental observations. It was a challenge to the physicists to find a way
out of this crisis. It was Neils Bohr, a Danish physicist, who in 1913 made some bold pro-
posals to meet the challenge of this baffling situation. He successfully used the Planck's
quantum theory to modify Rutherford's atom model. He put forward the concept of special
_orbits and quantization of energy of the ato~
Bohr atom model is based on certain post~lates.
Postulates of Bohr atom model·
(i) Bohr accepted Rutherford's concept of nuclear atom model, i.e., all the posit!ve paaj-
cles are concentrated at a QOint known as the nucleus and the electrons_are revolving

- - ----- ----- _,,..,

nucleus and the electron supplting ------:--"--.:-~- -
round the nucleus -in7 ir~ ;i-; -orbits; the-~lectro;-t;tic force of attraction between the
- to
.the necessary centripetal force for the electron
revolve -round
-
- -. the
.
nucleus. . .
(ii) The electron can move only in certain specified orbits which ~atisfy certain quantum
.

conditions. Only those orbits are allowed in which the angular momentum of the
electron is an integral multiple of h/21r; wh;~ h is th; Planck's const~i. ~ ie
moving along thej~9 rpi!§ _f.Q!!nd °ffie nutjeus, an electron does not radiate energy;
These non-radiating o~its ~e.called stationary orbits.
(iii) J?:mission ~r absorption of energy takes I?lace when an electron 'jumps' from one per-
mitted orbit to another. · - -
- --- - .
Let El and E 2 )Je the energies _o f an electron in an inner orbit and an outer orbit.
When the electron 'jumps' from the inner orbit to th~ outer orbit, it absorbs an energy, ·
/ .h11=E2-E 1
When the electron 'jumps' .from the outer orbit to the inner orbit, it emits an energy,
hv = E2 -E1 ./
:.11 = (E2 - Ei)/h. This is known as Bohr'sJ:e~ n~y ~ nditi?n.
Note:
*Wave mechanical model
de Broglie gave a physical interpretation of Bohr r
postulate that only certain orbits are permitted for the
electron. He treated electron as a wave of wavelength,
A = h/mv; where mis the mass and v the velocity of
the electron. Fig. 1
According to de Broglie concept ~f matt_er waves, a circular orbit is taken to be a
stationary state if its circumference contains an mtegral number of de Broglie wavelengths.

161
 ATOMIC STRL'CTlJ~E

ie wavelength then, the circumfere

· d ,\ the de B ro gl nee .
If r is the radius of the orbit an
and,\ =
h/rp,v.
' 21rr = n >. = n x }!_ ; where n 1, 2 , 3 , · · ·
=
l mv nh
.·. mvr= -27T"
. _ mr2 x (v/r) = mvr
Angular momentum of the electron, L = 1w - . . .
f electron in any orbit ts an mtegral multiple of
Thus the angular momentum o an . it as an ad hoc postulate in viol .
h/ 21r, same as that proposed by Bohr. He introduced ation
of the known ideas of classical physics.

/ Bohr's theory of hydrogen atom

V
According to Bohr's first postulate, the atom con-
(±)··· r ..:... -e
sists of central nucleus carrying the positive charge sur-
e m
rounded by electrons revolving in various· orbits. The
charge on the nucleus is Ze; where Z is the atomic num-
ber. In the case of hydrogen, the nucleus. carries a unit Fig. 2
positive charge e with one electron revolving round it.
The electrostatic force exerted by the nucleus on the electron supplies the centripetal force
for the electron to make the circular motion.
Since the nucleus is very heavy compared to electron it is reasonable to assume that
the nucleus remains at rest. Let m be the mass of the electron, v its velocity and r the radius
of the orbit. Then,
mv 2 1 exe 1 e2
- - = - - X - - = --X -
r 41rEo r2 · 41rEo r2
2 1
.·. mv r - x e2
=- (I )
47rEO
According to the Bohr postulate, angular momentum, or moment of momentum
L = n x h/21r; where n = 1, 2, 3 . ..
.·. mvr = n h/21r (2)
(n is called the principal quantum number)

Expression for the velocity (v) of the electron

Dividing equation (1) by (2), v

4
·~ x
e
2 /
. . 1rEo (nh/ 2ir) ·
Multtplymg the numerator and denominato Of th . . .
tion with c, the velocity of light, · r e nght hand side of the above equa

.
~= ~ [~
n 41rEo
C
X e2
(hc/21r)
l
l.e., v =- X o· (3)
n '
1 e2
where a= - - x - - - , is a dim · ·
41rEo (hc/21r) .... ens1onless constant kn nsra11t.
Substituting the numerical valu f own as fine stn,cture co
es o c, hand e it is t
For the first orbit, n = l , v = (l / lJ, ou nd that a = 1/ 137 _
7) c Th ·11 o!
hydrogen atom has ( 111 37) times the velo . : us the electron in the first orb
city of hght in vacu um.
ATOMlC STRUCTURE 163
Exprrssion Jar the radiu.r: (r) oj11t, p,rmiJttd orl,iJs . /
From N}UAtion (2), r ::-- n(b / 2 ,r)
m,,
Snh, t1t111mg the vnluc of,, from the equotion (3),
'1
r =~ x (h/ 2rr )
m co
Su1'-.11tutin~ the values of m, h, c and o . we get.
r = 5 .29 x 10- 11 n 1 = 0 .529 nl A
... r oc n 2
Expro'>"!,Wn for t1ie energy of the ekctron in the orbit ✓
Energy of the electron in the stationary orbit is partly potential and partly kinetic. /

2
e2
.
From eq. (1). m v
2
= - - :. K.E. = -1 x -1-
e
x -
4rrtor 2 41r£0 r
2
P.1!. (,f the electron in the orbit= _l_ x e(-e) = _ _l_ x e
41r£0 r 41rEo r
1owl cnerg~ of the electron in the nth orbit = K.E. + P.B.
1 e2 e2 1 1 e2
i.t., En= -
2
X -- -
47rfQT
--
47rEQT
= --2 X -- X -
47rfQ r
Suhstitutinp the value of r from equation (4)
1 1 moo
En = - - x - - X e2 X - .2 . - - - -
. 2 4rito n (h/21r)
1 mc'lo 1 e2
c:i - 2 x n 2 x 41rto x (hc/ 21r)
.·. Eu = - 2~ X mcnl2o 2 ( ·. _ l _ !,( e2
(hc/21r )
= a)
· 4irto
~uh~111u1 ing the \'WUCS of m = 9.11 :.c 10- 31 kg; c =3 x lO" m~- l; et = l / L~7 and
e..\.pres~n.g £ 11 in electron ,-olt. we get.
13.6 V
En = - --:re
n
for the firs.t orl>i1 n = l, £ 1 = - 13.6 cV
13.6
For rhe se:eond orbil n = 2. E2 = -
4 = -3.4 eV
13.6
/ for 1he third orbit n = 3. £ 3 = - 9 = - 1.51 e V

\, Significanc-e of n~galive energy of ,Jectron in an .orbiJ

n1e energy of 311 electron in me orbil of an atom is n~ga1i ve. For Hydrogen it is
- (1 3.6 t12) eV· where n = l. 2, 3 ... · l• shows lha1 electron 1s bound co the nucleus. The
gre:uer lhe va) u~ of ~egati,·e enei;gy, lhe greate_~is the bin~ing force ~tween the nucleus"aruf
lh~ electron. Since the electron in the first orbn has m.axunum negative energy, the binding
 164 Th b'10ding force decreasest for outer and
. . bo d 0 th
1s maximum. e · .
energy of the first orbit electron
the outerm ost orb it of an atom is leas~ un - . e nucleus.
outer orbits. The electron in
d- - - tOm, the energy needed 1s 13 6 eV' lc to
--
~ - - it-- e)e . ,.., • -
To release the nrst orb ctron from the hy rogen a to release
d
tluc orbit_electron,
energy req uired is 3.4 eV,
release the second orbit electron the '
-=-: .:- --
the energy needed is 1.51 eV and so on.
wave number of the spectral lines
Jiy dr og en spectrum: :::ivekngth and given
in ~e n ti\ orf?it of the hydrogen atom is
The energy associated with the electron
by, .
mc2o:2
1 fine structure con stant.
En = - x n 2 , where o is the
2 a tran sition from a higher ene rgy level n2 to a lower energy level
ff an e]ectron ma kes
be emitted
then acc ording to Bo hr's freq uen cy condition a photon of frequency v will
n1,
suc h that,
2 2
hv = En2 - En 1 = _!m c o: n~
2
[2- -2ny-J = ~mc2 a
2
2
[2-n?' -2-]
n~
.

. v ·= ~ x mch2o:2 [~2 -- 2
.. 2 n1 n2
2-] .
tte d then v _:_: ~
If A is the wave]ength of the radiation e~ A
2
. = ·Ac _- !2 x mc2ho: [ n21 - n21
··v 2
l
1

1= ~ xm:
2
[-; - -;]
n1 n 2
= RH [~
n
-
1
!_]
n~
.
l moo 2 Its value is
where RH = -2 -h- is a constant caJJed ·Rydberg constant for hydrogen atom.
1.09678 X 107 m - 1 .
denoted by v /
(1/ A) is called the wave nup1ber and is

. . . .. : .v = ~ = RH ( :1 _:~]
.
relatio obtam
This equation 1s s1mtlar to the empirical n ed by Rydberg earlier
·
Spectral series of hydrogen atom
./ be
( The hydrogen spectrum consists of a num r of series and each series consists of z
..
nes. A series is due to the ·trans1ti
munber of Ii~
energy states; T _e
.
lillp'Ii
ortant series are given
ons to a arf
belo w. P · icular energy state from higbe1

I. L~ an series:
d.
This series is in the ).J]traviolet r~i Q_0 is due to the transitions to the first orb
it
an
Hence n 1 = 1, n 2 = 2, 3, 4, . . . .
2. Balmer series:
This series is in the yisible reg.ion .
and is ..
. due to the tr
n - ans1tions to the 2nd orbit.
I - 2, n 2 === 3,·4, 5, 6, .. .
 ATOMIC S'fR UCT lJRE

Ghe re are four .imp orta nt-r

..
due to the trdilSttio
H from
nf
·
Ines m -t
h' • 7i · 165

3 d 2 1s sene s ·The y are H o:, Ha ' R-y and·Hc5 lines. Ha 1s_

-
·
8 6th to 2nd. rom r to nd state, /3 from 4th t<:_ 2~d, H from 5th to 2nd and
3. Paschen series: 7
This is ~ tbe infr ared ·r egio n and is due to the transitions to the 3rd orbit.

4. Brackett series:
-n2 = 4, 5, 6, ...
This is in the !_nfrared regi on and is due t~ the
transitions to the 4th orbit.

5. Pfund series:
This seri es is also in the infra red regi on and
is due to the transitions t~ the '5th orbi t.
!'1-2 = 6, 7,8, ...
Energy level dia.gram

The ener gy of the n th state of hydr ogen atom

is give n by En= - 13 ·6 eV J
. n2
The low er mos t state has ener gy -13. 6 eV. Tbi
s state is called grou nd ·state. The othe r
· . 13.6 . 13.6 13.6
states have ener gies - - 2- eV, - --i"- e V, - - - - e V and so on. When n = oo, E o.
~ Thus the ioni satio n ener i}, of hyd ro1e n atom
2
is 13.6' e
=
v::f.he
high er ener gy state s are calle d
excited sta t~ .. _ _· _. .
The diff eren t seri es expe rime ntal ly obse rveq
are repr esen ted on an ener gy leve l dia-
gram (Fig. 3).

0 2~ ........
........... ......... ······ ······ll······················· n = oo
:o:38 ·········· ·········· ········ . ······ j,······ ········~ · infra red
~0.54 ········ · ········ · ······ . .... · -'··pruoii···~~ffa
red
...... . ..... . .... ..... Series ............. n =4
1:~:!~ : : ·: · · hslf;~~i~~•~;d 1
~ Series .1
.£ ~v isi ble
6'D -3.4 .................................................... n= 2
t .. Balmer
Jj Series

~ Ultr avio let

-13 .6 ················ .................................... ......... .... n = I

Lym an
Series
Fig. 3
N cont ains only one electron
ote: !hou gh hyd roge n ato :as o~ly one electron revo , its emission spec trum consists of
lving round the nucleus. But it can
mh any Imes . Hyd roge n atoNro ally the electron
ave man y ener gy states. in the atom occupies the first orbit. When
orm
 ATOMIC STRUCTlJRE
166
out sid e it 'ju mp s' from the first
· th Orbit of the atom absorb s ene rgy from this' exc ite d sta te the atom is
the ele~tron m e states. 1n
' . , th
orbit, e groun d stat e to one o
f the hig her energy ctr on falls bac k to one of the
. ' . h' a time of about 10 -8 s' the e1e
not stable. Immediately, ~it m hot In a lig ht sou rce , ex: hydrogen
lower energy states releasmg a p on of definite frequenc~- the ato ms ma y be excited to
The electron 1ll
lamp, there are a large number of atoms.
. b
take pla ce. He nce we o ser ve man
different energy states and all pos sible tran siti ons can . y
.
lines in the hydrogen spe.ctrum.

Hydrogen like atoms

. . -(Li++ ) are similar to hyd
Singly ionised (He +) an d doubl ionised lithium rogen
y F an ato m of ato nu.c nu m ber z th
except for their greater nuc1ear cbarge· and mass. or ' e
. .
radius of the orb it, . h
. nuclear charge is Ze. Hence the
expression for the ene rgy etc. , s ou ld
.
~ modified. 5.27 X 10 -ll X n2
Radius of the n th orbit, Tn =
z
Velocity of electro~ in an orbit,
.
· . Z
vn = -C x ax·
n-
Energy of an electron in the nth O!b
it, -

En =
· -13 .6 x z2
eV
n2
Th e wave number of the spectral
line, ..

i7=!=Z2RH(22__2_2 ) J
A n1 n2
Limitations of Bohr's theory
Although Bo hr's theory was succes
sful in explaining various spe ctr
gen, it suffered the following lim al ser ies of hydro-
itations:
fa Both circular and elliptical orbit~
are . possible. Th e theory do es
• ::· answer to why circular orbits no t gi've any clear
are to be chosen. .
.9i) For hydrogen most of the spectral line
s are in fact groups of two or mo
close to each other. .Bohr's theory re lin es, very
does not explain this fact.
)ii i) The theory does not predict •
the intensity of the line. .
Jiiv) The theory failed in the case of ato
ms having large num ber of e)e ctr
ons .

EXAMPLES
Find the wa.velength of photon emitte
d when h dro
/ :to the ground state. RH .= .1.09 x _ A-
7 10 3 l Y gen atom goes from n-_ 1ostate
1 [12 - ·1- 1 -
-A = RH R f 1 l 1 [ . 1 1 . 99
n~ n1 - H l12 - = RH1()2
.X = 100 _ lOO
= 1- - -R H
100 100
99 R jr 99 X 1.097 x 10~ = 921 A
 C STRU CTUR E , 167
The wavel ength of .first line of Balme r series is 6563 A. Calcu late Ryd~ rg C!)n•
stant. . ·
!:_ = Rn [~ -
A nf n~
2-]
For first line of Balme r series, n 1 = 2 and n = 3
2

!= RH [ {2 - ;2 l =RH [ ¼- ~l =RH [ :6]

R · = 36 __, 36 _ . 7 _1
n 5.A - 5 X 6563 X l0-10 - l.0 97 X lO m

I./ Given ~y~be rg consta nt as 1.097 x 107m - 1 , find the. longest and shorte
st wave-
7 length limits of Lyma n series ·. ·

. .A
!:_ = Rn [2- -.1-]
n 21 n 22
(a) For longest wavelength limjt, n 1 = .1 and n2 = 2
!= RH
4
[i12 ~ ;2
·
l =RH[¼~¼]=
4 ..
R1t x
·
~
A =·-R
n
= · = 1.215 x 10-7 m = 1215 A
3 3 X 1.091 X 107 .
(b) For shortest wave len~ limit, n1 = 1, n2 = oo
.1A = [1 1] •= Rn
Rn 12 - 00

· ·.
· limii·
,\ = - l ·=
Rn
. . ·1
7
. 0 912 10- 7
= . x m = 912 1
A
' .

J
I.097 x 10 . ·
The series of Balme r series is 3646 A. Calculate the wavelength of the first
member of the series.
For Balme r series limit, n1 = 2 and n2 = oo

.!:_=Rn
,\ [2-ny -2-]
n~ =Rn[_!_ - _!_]] = Rn 22 oo 4
4 4
Rn · · .X = 3646 A
For first number of the series n 1 = 2 and n2 = 3
}:_=R
,\
n[_!_
22
-
1
32
] =RH
,
[!4 - !] = ~RH
9 36
_ ~ = 36 x 3646 = 6563 A.
.X- 5Rn 5x 4
Calculate the energy required to ionise hydrogen atoms in the ground state.
Given
Rn = 1.097 x .107 / m ; h = 6.63 x 10- 34 Js, c = 3 x 108 m 8 - 1 _
Energy required to ionise the atom is numerically equal to the energy of
the
electron in the ground state.
 Al vmn.., ..., 11'-ULTlJRB
168
Energy of electron in the ground state mca2]
1 mc2a 2 __ Rnhc; [since RH= 21 x-,;-
En = - 2 x n 2 - n2 .
For n = l .'. E = - Rn he 8
= -1.097 X 107 X 6.63 X 10_34 X 3 X 10 J
1.097 X 107 X 6.63 X 10·_34 X 3 X 108 eV = -13 6
1.6 x 10 19 . eV

Ionisation energy= 4-13.6 eV

4341 A. Find the wave.
1.6 The wavelength of ihe H, line in the hydrogen spectrum is
length of the 2nd line of the Paschen series.
According to Bohr's model, the wavelength.(A) of the emitted radiation when the
electron jumps from a higher energy level n2 ~o a lower energy level :n,1 is given by,

!_=RH[_!_ - _!__]
.X n~ n~ ·
H,,, line is the 3rd line of the Balmer series and is due to transitions from n = 5 to
n = 2 orbit. ·
1 . · [1 1] 21
. :. Al . RH 22 - 52 ·= 100 Rn (1)

Th~ second line of the Paschen series is_due to the transition from n 2 = 5 to n 1 = 3
orbit. · · ~ ·
. 1 [1 1] 16 . (2)
. . ·A2 = Rn 32 - 52 = 225-RH
Eqns: (1)/(2), .X2/ A1 = 21RH x 225
100 16RH
A _ 21 x 225 21 x 225 ·
• 2 - 100 x 16 x .X1 = 100 x 16 X 4341 = 12820 A
Calculate . of hydrogen
th~ time· taken by the electron to traverse the first orbit
atom.

The radius of the nth Bohr orbit

. 2
rn = n X 5.29 X 10-ll ID

. For the first orbit, n = l, r = 5.29 x 10-11 m

Velocity of the electron in the nth orb't _ ' -(- x - c
. l,V
137 n
For the first orbit, n = 1, V _ 1 x c - 3 x 10-B
- - - 13_7_
137 -
Period of electron in the fi rst orbit. · = _!!!_
2 _ 21rr x 137
V 3 X 1Q8
= 2 X 7T' X 5.29 X 10-ll X 137
3 X 108
The energy of an excited hyd == 1.517 x 10- 16 8
rogen atom .
s 1s - 3.4 eV Cal I th r n10·
mentum of th e electron accord·mg to Bohr's th · cu ate e angu Ia
eory.
ATOMIC STRUCTURE
169
The energy of the electron in the th .
n orbit of hydrogen atom,
En = - 13.6
13.6 .
n2
eV.
.. n = 2
,
-3 4 -
• - - -2-
n
Angular momentum, L = nh _ 2 x 6.625 x 10-34
·21r - 2 X 3.14
_ = 2.11 X lQ- 34 J s
I.9 Using Bohr's formula for ene . .
n = 3 level of He + atom (..) ~ . quantisstion determine (i) excitation energy of
11 mrusation potential 0 f d ++
(Given RH = 1.097. x 101 /m) groun state of Li atom

. .·d
(i) Energy of the nth state· of 10ruse :·
. atoms

En= z2 (-:~· 6 ) eV
For He++ atom z =2
E 2 -13.6
1 =2 x
12
= -54.4 eV
2 -13.6
E3 =2 x
32
= -6.04 eV
Excitation energy from n .= 1 to n =3
= -6.04 ~ (--:-54.4) = 48.36 e V
2 6
· (ii) En= Z (-:~· ) eV

13 6 122
For Lithium Z = 3, En= 32 (. -_n2 · ) = ~
n2
· .4 eV

Energy in the ground state = -122.4 eV

Ionisation energy= +122.4 eV; · Ionisation potential = 122.4 v

BOHR'S co~SPONDENCE PRINCIPLE

.. ;, . ¥' •

In 1913, Bohr suggested a specific model of the hydrogen atom which, in spite of
Certain defects, proved to be a major step towards the understanding of the atomic struc-
ture. Bohr succeeded in extending the applications of Pl~ck's quantum principles to the
Rutherford atom model. He accepted Rutherford's nuclear atom model in which the elec-
trons move around he nucleus in circular orbits. According to the classical electromagnetic
theory, any accelerating electric ~harge (either oscillating or revolving) radiates electromag-
netic wav~s of frequency equal to the frequency 0f the tevolving charge. Hence the energy
of the orbiting electron should decrease continuously, its orbit should become smaller and
smaller, and it should spiral rapidly into the nucleus.
Bohr made a revolutionary propos1;1l to solve the problem. He postulated that an elec-
tron in an atom could move around the nucleus only in certain circular stable orbits, without .
emitting radiation, contrary to the predictions of the cla~sical electromagnetic theory. Ac-
cording to Bohr, these stable orbits are governed by certain quantum conditions and there is
 ATOMIC STRUCTl.JR.E
170 . . bl bit and an atom radiates energy onl
a defirute energy associated with each sta e or . . YWhen
it makes a transition from one of these orbits to another. The energy is radiated as a Photo
of frequency v given by hv = E2 - E1; where E1 and E2 are tbe energies of the Otbi~
between which the transition takes place.
Bohr's corresl'°ndence principle establishes a co~la~on_ between ~e results ob~
from classical and quantum theories. According to this pnnc1ple, the higher the qua
. d ad' . fi · nturn
number
. the more nearly does the frequency of the emitte l ,., iatwn
. hor a transition from one
or it to the next below, approach the frequency of the e ectron zn t e orbit. In other words
b
w~n the quantum number involved is large the Bohr frequency approaches the frequ,
wluch the atom would emit_according to classical theory. · ncy,
The radius of the nth orbit is given by,
2
T - _n_h_ • where h = Planck's constant
n-:- 21rmca'
m = mass of electron
/

c = velocity of light
e2
and a -~ -:-----
4m:o(hc/21r), ·the fi ne structure constant.
The velocity of e~~tron in the nth orbit is give~ by
C
Vn= -a
The period of revolution of the electron in the nnth orb.1t 1s
. given
. . by
T= 21rrn
Vn

Orbital frequency, Vorb = ..!:_ = ~

T 21rrn .·
= .:. 0 x 21rmca mc2 a.2
2
The energy of the nth orbit is given by n 21rn h = n3h

E= _! x mc2a2
The B~'s frequency when a transition 2 n2
an orbit of quantum
· number n1 m
. given
. takes
by, place from an orbit
. · of quantum number n t<

IIB9hr = En-En1 1 me2 a2 [ 1

. h
-
- 2 h 2 - ...!_]. -mc2 a2 (n n2]2 -
The ratio of the frequencies i.e.,
. nl n2 - 2h 1 21
n2n
Orbital freque
B ncy - m c2a2
ohr frequency - ~ 3 - x
. h (~2~~2~- -
2hn~n2
n - n1) m c2a2
· :::::: _ 2n~n2
3
When n and n1 are large and n _ n1::::: 1 n (n + ni)( n _ n1 )
, then n2 2
. .Orbital
·. fr ~ 1n ~ n4 and n +·n1 = 2n
Bohr frequenc ::::: - 2n4
y n 3 X 2- - = 1
nx 1
 ATOMIC'STRrTCTURE o l.- ' Ht
~ us ihe orbital frequency · ap~ro·acnes tfie Bohr frequency when _the qu~t u~ lll!_~r is
l-rarge. This is the limit chani~terized by large quantum numb ers, \Yh~
clas_s~cal_PE~..!.cs~d
~ m phy~ics lead to.the same. p,ceqictio_!!s . .11tl~was p~inted_ E}l! ~Y.Bo
hr.ip 1923 ~ n~-~s
.know~ Bohr's correspond_~nce principle. J · ·' ·
Note:- Sommerfeld's relativistic atom model
·,
In order to overcome the ·shortcomings of Bohr~s· atom model, Somm
erfeld ·modified
B_ohr's model.by introducing the idea of elliptical orbits and taking into
actou nt the variation
of mass with velocity.

. VECTOR ATOM MODEL

.

The Bohr-Sommerfeld model of the atom despite accounting for the

spectral proper-
.ties of hydrogen atom is not a complete description of the atomic structu
re. The following
are the major drawbacks of the model.

(i) Original Bohr' s theory was incapable of explaining the fine

structure of the spectral
lines even in the simplest hydrogen itom. ·
·
(ii) The Bohr theory is applicable only in_the case of one-electron
atoms such as hydrogen,
singly ionized helium etc. _It f~_!s to explain the spectra of complex atoms
.
(iii)_Sommerfeld's modification, thoui h-ga~~-; th~oreticai backgr~~~d
of the splitting of
the individual spectral lines of hydrogen, still it could not predict the
correct number
of observed fine structure of these lines.
(iv) These·models could not explain the distribution and arrangement of
-- - .....
(~ These models do not throw light on the intensities of the spectral
-:-------
electrons in atoms.
. .. - - - ··- ....-~--

lines.
~) Both the models failed to explain the effect of magnetic field on·
spectral lines, such
as anomalous Zeem an effect and Stark effect. .

To overcome all these objections a new model known as vector atom

model was pro-.
posed by Uhlenbeck, Goud smit and others.
The two concepts which characterise the vector atom model and differe
ntiate it from
the other models are: ( 1) the concept of spatial quantisation; and (2) the
concept of spinning
of the electron.
,.,,
Spatial quantisation
According to Bohr- Somm erfeld theory the s!!_ape <!Ild the_si'.?~ of the
orbit~) ![~_qqao.-
~ed. But according to quant um theory their' orientation also should
be quantised. Ac-
cording to the old theory: the orbit could point in any direction; howev
er acc.2!_ding ! <?,pie .
. quantum theory; the axis o~ the ·orbit may point only .i.n·ue .w.p~ ~rred
directio~s:· these
----
dirnetinns are determined by the direction of any external fore~ that may"b
-~-- ---- - ,. .. ~
a ~. Thus according to the quant u.,.P theory both magnitude and direct ~,
e"acting 'On the
............
ion ~f th~ or~~!,S are
quanti
__.- sed. The introd uction 'of such-a ·s pace quantisation makes.the orbits vector quantities.
. ;

Spinning of the electron

.
The electron orbiti ng the nucleus also spins about its own axjs. Since. ' . '
the electron has
. charge, the spinning of the electron is equivalent to an electric circui
t and hence a magnetic
moment'is associated with it.
172 ATOMIC STRUCTlJR.e

Accordingly 'the angular momentu m of the atom will now be due to drbital rnot·
- - - - , · •on
. . -------- -...
~---
and spin motion ..,,.of the electron. . . . . .. .
. According to quantum theory,.· like .orbital m~ n, s?m, ~~~ ts also quantised
Hence a new quantumnumbei known as.spiicquantum numoer IS mtroduced. , - - - fl·
, . -t
Orbital angular momentum I 1~ : ' .., ) ">.

. In Bohr's theory, the angular momentum of the el~ctron is quantised. Angular rn~
mentum = nh/2rr where n is an integer. In Sommerfeld theory, the angular momentum is
represented by kh/2rr; where k is the azymuthal quantum number. In vector atom model k
is replaced by l which is know as orbital quantum number. The orbital angular mo_~enturn,
Pz = l(h/2rr); · where l = 0, l, 2, 3, etc.
The orbital angular momentum is a vector quantity. The value of l can take any
integral value betweenJLang (_n = l) \ where n is the principal quantum number. It is a
common practice to assign letters to l values as shown below: . · .

0 1 2 3 4 5
Orbital quantum number · l
p· d f g h
Electron designation
Here the letters s, p, d, f stand for Sharp, Principal, Diffuse, Fundamental etc.

Electron spin angular molnentum

Due to the spinning of the electron it has spin angular momentum. It is given by,
P8 = s(h/ 2rr) wheres = ±1/2

Total angular momentum of electron

We have seen that an electron has orbital angular momentum Pz and spin ?J}gular
_momentum Ps. The total angular momentum of a single electron is the vector sum of the
orbital and spin angular momenta of the single electron. The total angular momentum is
given by,
Pj = j(h/2rr), where j is called total angular momentum quantum number.
- ...
~ -~
The value of j are j = l + s and j = l - s with the restriction that j mu~t be positive.

QUANTUM NUMBERS ASSOCIATED WITH THE VECTOR ATOM MODEL

The quantum numbers associated with each of the electrons in a given -atom are the
following :
1. The principal quantum number (n) . ·

Grus quantum number belongs to the principal orbit to which the electron belongs and
is identical to that used in Bohr-Sommerfeld them~tak~ only integral values excluding
zero. The angular momentum of the electron in the orbit is nh/2rr.
2. Orbital quantum number ([) e: ;-

-Grus quantum number defines the shape .of the .orbital occupied by the electron and
the orbital angular momentum of the electron. This takes all integral values from zero to
(n - I). Each value refers .to an energy subshell. .
= ---
AT()MIC STRUCTURE 173

Orbitals having the same value Of n but · •

di diffi different values of l have various energy
quantum number also refers to the degree
values c~rrespon ng to. erent values of l. The
with which the electron 1s atta ch~ to the nucleus.

3. The spin quantum number (8 )

for the spin of the electron about
this q~antum num ~r has _been introduced to acco.unt
_e the electron can spin in clock-wise .or
their own ·axJS. The magrutud~ is always 1/2. Sinc
n to 8 i.e., +~ or: -~ ·
anti ciock~wise directions there are two values give
ys, ·
The angular momentum due to electron spin is alwa
sh 1 h
Ps =- =- x-
211" 2 211"

4. The total angular quantum number (j)

·spin angular momenta. If these two
This is the vector sum of the electron's orbital and
the opposite directi6n' it is l - s. The total
act in the same direction it is l + s; if they act in
angular momentum,
. h
Pj = J X 211"

equently split into two levels with

Every l level except that for which l = 0 is cons
e·of spectral lines although the number'of
different energies. This explains the fine structur
lines is limited by selection rule 6.j = 0 or ±1.

S. Magnetic orbital quantum number (ml )

, the electrons with the same val_ues
When an atom is placed in a strong magnetic field
unt for this, one more quantum number
of n and l may still differ in their behaviour. To acco
mt known as magnetic quantum number
is introduced.
l along the direction of the magnetic
The projection of the orbital quantum number
Since the projection also is quantised mz
field is the magnetic orbital quantum number mz.
can take only integral values given by

l, (l - 1), (l - 2), ... , + 1, 0, -1; -2, ... , -l

be inclined to the magneti c field

This means that the orbital angular momentum can ·
ple if'(} is the angle between the l-vector and !f
H only at certain specified angle. For exam
would give . ·.
direction, then (} ccµi take only such values which

m1 = lcosB = l,l -1, l - 2, ... , 1,0, -1, -2, ~.. , -l

For examp]e if l = 2, m, can take values 2, 1, 0, -1_and -2. Hence l vect

or can have
d
5 directions. If l = 3, m 1 can take value 3, 2, 1, 0, -1, -2, -3. There are seven pennitte
n. It impli~s that the.space around H has
Orientations. This is known as spatial quantisatio
is forced to take up only certain
acquired some peculiar property by which the l vector
SJ>ecified directions.
 174 ATOMIC STRt:Jc'
H +3 H
m,=2
+2

;
m,=o 0

) -1
m, =-1
-2
-3

/= 2 /= 3
Fig. 4

6. Magnetic spin quantum number (m 8 )

This is the -projection of the spin quantum nµmber (s) in the field _direction. Since the
value of sis always 1/2, ms can take only two values 1/2 and -1/2. ·

7. Magnetic total angular momentum quantum number (mj)

Its numerical value is the projection of the total angular momentum vector j _on the
field direction. Since j can have half integral values, mj can have half integral values. The
possible values are - j to +j excluding zero. ·
1 . 1 11 1 1
If l = 2 ands= 1/2 then j = 2- and mj can take six values 2-2 , 1- , -, -- , -1-,
. 2 2 2 2 2
1. .
-2-
2·
The.quantum numbers explained above refer to the state of a single electron. lfthe
quantized vectors· of all the electrons in an atom are suitably combined we get the quantised
vector for the whole atom. The small letters l, s, f and s, p, d, f are used to indicate the
state of ~electro n and tbe capital letters L, S, J and S, P, D, F etc are used to indicate_the
state of the atom.
C~upling Schemes
The orbital and spin motions of the elect;rons produce magnetic fields·whi<;h mutually ·
interact with each other and with similar fields produced by other electrons, if any present
in the atom. In order to get the vectors representing the atom as a whole, the combination
of different ·vectors of the electrons sh~uld be worked out and thi~ may be done in .several
ways depending on the 'coupling' between the component vectors. Generally two types of
coupling known as Russel-Saunders or L-S coupling atJ,d j-j-coupling occur.
he L-S Coupling . .

/ This type of coupling occurs most frequently and h~nce known as normal coupling.
In this coupling all the l vectors of the electrons combine to. form the L vector and all tbe
·s ·vectors combine to form the S vector. Now the vectors Land S combine to form the J
vector.
 ATOMIC STRUCTURE · 175
Here L· is always. an integer
. • ;.e., o, 1, 2, 3 etc. The value of
· S depends on the number
of electrons and ~e direction of the spin vectors. _S is an integer for ·an even number of
electrons and half mteger for odd number of electrons.
Since J is the
. . sum of L and S 1·1 wouId take mtegral
· ·
or half mtegral ·
values depending
upon whether S is mtegral or half integral. However J is always positive as it represents the
total angular momentum of ~e atoms. . = .

f,
J· · Coupling · .
Sometimes the intera~tion between spin and orbital ~ectors of each electron may be
stronger than that between either the spin vectors or the orbital vectors of different electrons.
In such.a case j-j coupling is more suitable than L-S coupling.
In j-j coupling, each electron is considered separately and total angular momentum is
obtained by the relation j = l + s. Then for the atom as a whole the total angular momentum
vector J is taken as the vector sum of all the j vectors of the electrons. Pure j-j coupling is
seldom found. . · ·

Electron configuration·of atoms •

In 1871 the Russian Scientist Mendeleev arranged different elements found in nature
according to their chemical properties and atomic weights. This arrangement was perfected
by spectroscopic studies. Mosleys work on characteristic x-ray spectra of elements estab-
lished that it is the atomic number and not the atomic weight which determine its position
in the arrangement. When elements were arranged according to their atomic number it was
found that the chemical and spectral properties of elements went on changing in an orderly
fashion upto a certain number and then started repeating in the same order in a periodic
manner. Hence the arrangement of elements is known as the periodic table.
This table of elements consists of seven horizontal rows called periods and eight ver-
tical columns called groups. As we go from left to right in the same period the physical and
chemical properties vary gradually as the atomic number increases. When we take the next
horizontal row we find their physical and chemical properties vary·similar to the one in the
above row. The elements-in the vertical column (groups) have very similar properties. ·we
can infer that electrons are arranged around the nucleus in orbits in certain regular order.
A study of X-ray spectra revealed that electrons in an atom are arranged in different
shells around the nucleus. The inner most shell is called K shell, the next one L shell,
M shell etc. When the innermost shell is completely filled with electrons the next shell
_starts filling up step by step. ·
To find out the number of electrons required to complete each shell we can make use
of the occurrence of the inert gases.at the end of each period. These are helium, neon, argon;
krypton, xenon and radon with atomic numbers 2, 10, 18, 36, 54, and 86. They are all mo_no ·
atomic. Rydberg showed that the number of electrons in an atom of these inert gases can
be arranged as follows. · .
Helium 2(1 2 ) =2
Neon . 2(1 2 + 22 ) = 10
Argon 2(1 2 + 22 + 22 )= 18
 176 ATOMIC STRUCTURE

2
Krypton 2(1 2 + 22 + 32 + 2 ) = 30
Xenon 2(1 2 + 22 + 32 + 3
2
+ 22 ) == 54
2 2 2
Radon 2(1 2 + 22 + 32 + 4 + 3 + 2 ) = 86
From this it is evident that the electrons around the nucleus can be arranged in different .
shells.
The vector atom model gives a rational explanation of these empirically derived prop-
erties of atoms.
Pauli's exclusion principle
The state of un electron can be specified by four quantum numbers n, l, m1, m,,. The
principal ·quantum number n gives the size ot' the electron orbital or the position of the
electron in the principal energy level; l gives the size of the orbital, rn1 the orientation of
the orbital and m,, the spin of the electron.
Puuli 's exclusion principle imposes cerwin restrictions on the four quantum num-
bers. According to this principle "no two electron.\' in an atom can ha,ve the same .,et of
four Identical quantum numbers". They must differ at least in one. Jf two electrons do
hove oil their four quantum numbers identical, then one of these two electrons would be
excluded from entering into the coni,;titution of the atom. Hence the name excluRion princi-
ple.
According to this principle the maximum number of electrons that can be included in
each shell can be calculated.

Principal Orbital Magnetic orbital Magnetic .,pin No. of

quantum numbtr quantum number quantum number quantum number electrons
n. l m1 · m8
IK Os 0 2
2' - 2
1 1
2L Os 0
2' - 2
1 1
Ip 1, +o, - 1
2' - 2
3M 1 1
Os 0 2
2' - 2
1 1
Ip +1, 0, - l 6 18
2' - 2
2d
1 l
+2, +1,0, - 1, - 2 2' - 2 10
T~us the vector ntom model gives a rationul explanation of these empiricully derived
prope111es of the_atom showing why electrons are arranged in shells, the maximum num-
~ of electrons m each shell, Hub shell, and how chemical, physical and spectral proper-
ues depend upon the electrons in the outemtORt shell and several other. propertie8 of the
atom.