UNIT I : ATOMIC PHYSICS

ATOM MODELS:
 Faradays Model: First modern conception of atom
 Discovery– Electrolysis of atom.
 Fixed quantity of positive and negative
charge of equal magnitude.

 [Link] Model:
 Idea of intrinsic nature of atom
 Discovery—Electron ,e/m of electron, electrical nature of matter.
 Entry of electron in atom
 Atom electrically neutral
 Uniform distribution of positive charge over atomic dimension
 Account for first observed spectra of element
 Electros were arranged inside positive sphere
ATOM MODELS:
 Rutherford Atom Model:The nuclear atom model
 Resulted from scattering of  particles by thin sheet
 Concept of nucleus
 Fails to explain the stability of atom
 Bohr Atom Model:
 Nature of orbit of electrons revolves round nucleus
 Explanation of origin of spectral lines
 Sommerfeld Atom Model: Relastivistic atom model
 Fine structure of spectral line
 Elliptical orbits
THE VECTOR ATOM MODEL:
 Extension of Ruterford-Bohr-Sommerfeld model.
 Bohr model explains series of spectra of H atom not fine
structure.
 Sommerfeld model explains fine structure but not about
relative intensities and complex spectra of alkali metals
 Old theories inadequate new discoveries Zeeman and Stark
effect.
 To explain distribution of orbital electrons
 Complex spectra of atom and relations with atomic structure
 The vector atom model basically deals with the total
angular momentum of an atom which is results of the
combination of orbital & spin angular momentum.
The vector atom model:
Important features of vector atom model
(A) Spatial/Space quantization :
(B) Spinning electron hypothesis :
(A) Spatial/Space quantization :
Bohrs theory-- Orbits are quantized.
Quantum theory—Direction or orientation of orbits in space
also quantized
To specify orientation of electrons orbit in space need fixed
reference axis
Direction of axis is direction of external magnetic field
Different permitted orientations electron orbit determined by
projection of quantized orbit on field direction [Link]
SPINNING ELECTRON:
 Introduced by Uhlenbeck and Goudsmith in 1926
 Fine structure and anomalus Zeeman effect
 Hypothesis- electron spins about an axis of its own
 Also revolve around nucleus –analogues to planets
 Quantum mechanics-spin of electron quantized
 Idea of spatial quantization –Orbital and spin motions are
quantized.
 The orbital & spin motion both are quantized in
magnitude & direction because they are considered as
quantized vector.
 Hence the atom model based on this quantized vectors
is called as vector atom model.

QUANTUM NUMBER ASSOCIATED WITH
VECTOR ATOM MODEL :
(1)Principal quantum no. (n) :
The serial no. of the shell’s starting from the inner most
is designated as its principal quantum no.
It can take only integral values excluding zero i.e.
n = 1,2,3,4 _ _ _ _ _
(2)Orbital quantum no. (l) :

This may take value any integral value 0,1,2,3,4, _ _ _ (n-1).

If n=4 l can have four values 0,1,2,3,4
(a) An electron for which l=0 , then it is s- electron .
(b) An electron for which l=1 , then it is p- electron .
(c ) An electron for which l=2 , then it is d electron .
( d) An electron for which l=3 , then it is f electron .
➢ The orbital angular momentum

The orbital angular momentum is

(3) Spin quantum no. :

This has only one value take ½ the spin angular momentum
p s = sћ
p s = s . h/2π
Represents total angular momentum of the electron
which sum of the orbital angular momentum & spin
angular momentum .
The vector J is defined by equation
j= l + s
j is always positive
Spin angular momentum s = ± 1/2
therefore j = l ± s
for e.g. l=2 & s=1/2
j= l+s for s is parallel to l
and j = l-s for s is antiparallel to l
j = 5/2 & 3/2
 The projection of the orbital quantum no. ( l )
the magnetic filed direction is called as magnetic orbital
quantum no.
The possible ml values are l, l-1, l-2, …….0,-1,-2,…-l
There are (2l+1) possible values of ml
for e.g.
l=3 → 3,2,1,0,-1,-2,-3
ml = (2l+1)
= (2×3+1) = 7
Permitted orientations of l are 7 for which
ml=3,2,1,0,-1,-2,-3
(6) Magnetic Spin quantum no. :
 This is the projection of the spin vector s along the
direction of the mag. field .
 The spin angular momentum s can assume only two
possible positions with respect to the magnetic field it
may be parallel or anti parallel .
 ms can have only two values +1/2 or -1/2 .
(7) Magnetic total angular momentum quantum no(mj).:

 This is the projection of total angular momentum vector j

on the direction of the magnetic field .
 For single electron j can have only odd half integral
values
j= l ± ½
mj must have only odd half integral values
mj can have only (2j+1) values
From +j to –j zero excluding
Coupling Scheme :

 In atom having two or more electron , the orbital &

spin angular momentum of all its electrons can be
added together in two ways .
 The method combination depend on the interaction or
coupling between the orbital & spin angular
momentum .
 There are two types of scheme have been developed
they are
(1) L-S coupling :
(2) j-j coupling :
L-S coupling :
 Occurs frequently so normal coupling.
 All orbital angular momentum vectors of the various
electrons combine to form a resultant L &
independently all their spin
angular momentum vectors
combine to form the resultant S .
These resultants L&S then
combine to form the total
angular momentum J of the atom.
 This scheme may be summarized as follows
L=∑ li S=∑ si → J=L+S,
L is always an integer including zero & S is an integer
for an even number of electrons & odd multiple of ½
multiple of ½ for an no. of electrons .

Hence, J must be an integer , if S is an integer & J

must be an odd multiple of ½ .
 In particular , if L=0, J can have only one value namely
 J=L+S → J=S
2 electron 3 electron 4 electron
↑ ↑↓ ↑ ↑ ↓ ↑ ↑↓ ↑ ↓
↑ ↑ ↑ ↑ ↑ ↑ ↓
↑ ↑ ↑
↑

S = 1,0 s = 3/2 , ½ s = 2,1,0

S = │S1 + S2 │ S = │S1 + S2 │ S = ½, 1/2, 1/2,1/2
to to S = (1,0) (1,0)
│S1 - S2 │
│S1 - S2 │ S = (1,0) (1/2)
S = (2,1,0)

S = (1,0) S = 3/2, 1/2

j-j coupling :
 This method is employed when the interaction between the
spin & orbital vectors of each electron is stronger than the
interaction between either the spin vectors or the orbital
vectors of the different electron.
The orbital & spin angular momentum of each electron in
the atom are added to obtain the resultant angular
momentum of the electron .
j-j coupling
 Thus ,
j i =l i + s i The vectors sum of all the individual j
vectors gives the total angular momentum J of the
atom .
Thus J = ∑ ji
[(l1+s1)+(l2+s2)+(l3+s3)+……]
= j1+j2+j3+…=J
Pauli Exclusion Principle :
 Statement : No two electrons in atom exist in the same
quantum state .
OR
“Every completely defined quantum state in an atom can be
occupied by only one electron

The four quantum state numbers n , l , ml, ms determine the state of

an electron completely . Hence the principle may be stated as “ No two
electrons in an isolated atom may have the same four quantum
numbers” .

❖ If two electrons have all their quantum numbers identical , then

one of those two electrons would be excluded from entering in to
the constitution of the atom . Hence the name Exclusion
Principle .
Pauli’s exclusion principle explains:
 Fundamental and universal

 Occurrence or nonoccurrence of spectral lines in optical and

X-ray spectra

 Complete scheme of arrangement of atoms in periodic table

.
 Explanation of electronic structure and atomic spectra

 Defining the special quantum property of closed shells

 e.g. k – shell
n=1 , l=0 & hence ml = 0 , since
s=1/2 ms = +1/2 or -1/2
Hence k – shell can have two electrons
for electron – 1 with quantum numbers ,
n=1 , l=0 , ml = 0 , ms = +1/2
for electron – 2 with quantum number ,
n=1 , l=0 , ml = 0 , ms = -1/2
 Max. no. of electrons in a sub shell is 2(2l+1) of l

 Orbital quantum no . (l) : 0 1 2 3 4

 No. of possible electron state : 2 6 10 14 18

❖ Sub-shell symbol : s p d f g

❖ Distribution of electrons in a shell with n=sum of electrons in

constituents n subshells

❖ Shell symbol : K L M N O

❖ Quantum no.(n) : 1 2 3 4 5

❖ No. of electron (2n2 ) : 2 8 18 32 50

Selection rules :
It is experimentally found that all possible combinations of permitted
energy states of an atom do not appear as spectral line.
Selection rules are principle, which give reason for such a state of
affairs.
For vector atom model three selection rules one each for L,J and S
Selection Rule for L :
Most of the observed spectral lines are due to transition between state
In which a single electron jump from one orbit to another
The selection rule is L=1 i.e. Only those lines are observed for
which the value of L changes by 1
Selection Rule for J :
Spectral lines arises only when transition takes place between states
for which J=1 Or 0, 0 → 0 being excluded
Selection rule for S:
 Selection rule for S is S=0 i.e. States with different S
do not combine with one another .
 This rule is good for light atoms
 Helps in allocation of observed spectral series to proper
quantum numbers.
 Energy level diagram can be constructed
Intensity Rules:
 Supplement to selection rule
 Predict intensity of lines that occurs
 Postulated on empirical basis in the study of optical and
X-ray spectra.
 Rules are:
 a) Those transitions are strong, give rise to intense line in
which L and J changes in the same sense
 The transitions are weaker, more the change in direction
of L and J is different.
 b) Transition in the decreasing sense (L →L-1) is stronger
 Than increasing sense (L →L+1)
 c)The oppositely directed transitions do not occur

Intensity Rules:
 L= -1 , J= -1 Most intense line (a)
 L= -1 , J= 0 Less intense line (a)
 L= +1 , J= +1 Weaker line (b)
 L= -1 , J=0 Weakest line (a and b)

 L= -1 , J= +1 No line (c)

 L= +1 , J= -1 No line (c)
 Interval Rule:
 Called Lande Rule
 Statement: Frequency interval between two levels with
two angular momenta (J+1) and J respectively
proportional to (J+1)
(1) The selection rule for L is ∆L = ±1 i.e. only those lines
are observed for which the value of L changes by ±1 .
e.g. L can changes from 0 to 1 (∆L = 1) from 1 to 0 (∆L = -
1).
(2) In symbol , a transition is possible between S & P levels
(∆L = ± 1) , but not possible between S & D levels
(∆L = ± 2) .
(3) The selection rule for J is ∆J = ±1 or 0 but 0→0 is
excluded .
(4) The selection rule for S is given by ∆S = 0.
 Zeeman effect :

 Zeeman effect is magneto-Optical

phenomenon
 Zeeman effect :a source of light
producing line spectra (spectrum )
is placed in a magnetic field , the
spectral lines are split up into
components.
 When the splitting occurs into two or three lines , it is called
normal Zeeman effect . The splitting of spectral line of
magnetic field is strong.
 The splitting of spectral line into more than three
components in ordinary weak magnetic field is called
Anomalous Zeeman effect.
Experimental arrangement :
 MM is an electromagnet capable of producing a very strong
magnetic field .
 Its conical pole pieces PP have longitudinal holes drilled
through them .
 A source of light (L) emitting line spectrum ( e.g. sodium
vapors lamp ) is placed between the pole pieces.
 The spectral lines are observed with the help of a
spectrograph (S) of high resolving power .
 the Zeeman effect may be observed in two ways :
(A) the positions of the spectral line is noted without
applying the magnetic field .
 The mag. Field is now switched on & the spectral line is
viewed longitudinally through the hole drilled in the pole
pieces & hence parallel to the direction of the field .
 It is found that the spectral line in split into two components
one slightly shorter in wavelength than original line.
 The original line is not present .
 Both the lines are found to be circularly polarized in
opposite directions . This is called normal longitudinal
Zeeman effect.
 (B) The spectral line is then viewed transversely i.e.
perpendicular to the direction of the magnetic field .
 In this case , the single spectral line is split up into three
components when the magnetic field is applied the central
line has the same wavelength as the original line & is plane
polarized with vibrations parallel to field.
 The displacement of either outer line from the central line is
known as Zeeman shift.
 The two outer lines are also plane polarized having
vibrations in a directions perpendicular to the field . this is
called normal transverse Zeeman effect.
 Consider an electron moving in a circular orbit or radius r
with linear velocity v & angular velocity ω
 The centripetal force acting on the electron towards the
centre is

F = mv2 / r = m ω2 r2 /r = m r ω2

If the electron in motion clockwise then the force Bev is

outward & if the electron motion anti-clockwise then the
force is inward.
m r ω2 – Bev = m(ω+dω)2 r
m r ω2 – Bev = m(ω2 + 2ωdω + dω2 )
as dω is very small , dω2 is neglected .
 m r ω2 – Bev = m(ω2 + 2ωdω ) r
m r ω2 – Bev = m r ω2 + 2mωdωr
– Bev = 2mωdωr (v=rω)
-B e rω = 2mrωdω
- B e = 2mdω
dω = - B e / 2m …………(1)
for clockwise moving electron
dω = B e / 2m …………(2)
dω = ± B e / 2m …………(3)

If ʋ is frequency of revolution of electron then ,

ω=2πʋ
dω = 2 π dυ
dυ = dω/2π [ dω = ± B e / 2m ]
dυ = ± B e / 2m 2π
dυ = ± B e / 4πm
 This gives the change in frequency the spectral lines.
 If υ & λ are the frequency & wavelength of the original line
then .
υ=c/λ
dυ = - c / λ2 dλ
dλ = -λ2 / c dυ
dλ = -λ2 / c ( ± Be/4πm)
dλ = ± Be λ2 / 4πmc

dλ – is the Zeeman Shift

STARK EFFECT :
 The Stark effect is the electrical
analogue of the Zeeman effect .

 The Stark effect is the

splitting of spectral lines due
to the action of an external
electric field on the radiating
substance .
The Stark line splitting is vey
minute & can be observed only
with instruments having a high
resolving power .
(a) Experimental study :
 Hydrogen atoms emitting spectral lines are subjected to a
powerful electric field.
 The canal rays are produced in an ordinary glass discharge
tube provided with a perforated cathode C .
 When the pressure in the tube is not very low, discharge
takes place between the cathode C & Anode A maintained
at a suitable P.D.
 An auxiliary electrode F is placed parallel & close to C at
a distance of a few millimeters.
 A very strong electric field of several thousand volts per
meter is , maintained between F & C . The effect produced
can be studied both transversely in fig. (a) &
longitudinally in fig . (b)
Results :
 The result obtained with lines of Balmer series of H atom as
follows
 Every line is split up in to a number of sharp components .
 All hydrogen lines from symmetrical patterns .
 The patterns depends on the quantum number n of the term
involved .
 The number of the lines & total width of the patterns increases
with n .
 Observation perpendicular to the direction of the electric field
transverse view shows that the components are polarized .
 Up to fields of about 107 v/m , the resolutions increases in
proportion to the field strength (E) . In this region , we have
linear or first order Stark effect . When E exceeds 107 v/m there
are shifts in the line patterns which are proportional to E2 & it is
called second order Stark effect .
ANOMALOUS ZEEMAN EFFECT:
 Effect can be explained using idea of spin of electron.
 The total angular momentum vector j=l+s i)
 Magnetic moment due to orbital motion of electron
•

  is opposite to l because of
negative charge
 Magnetic moment due to spin of electron

 s is directed opposite to S
AZE
 Resultant magnetic moment 
not along j
To find resultant l and s resolved into
two components one along j and
Perpendicular to it.
Perpendicular components are cancelled
The effective [Link] of electron is
= j =components of l along j
+components of s along j
 AZE


 but according to cosine law

aze
 Writing

But bracket term is g i. [Link] factor

If atom is in weak magnetic field, total angular momentum

vector j precesses about direction of magnetic field as axis
The additional energy  due to atomic magnet is
AZE
 But J cos (j,B) is projection of vector j on direction of
[Link]=mj