SOMMERFELDMODEL OFTHE ATOM

The modifications made by sonmmerfeld to the Bohr model are

1. The clectron moves in elliptical orbits with nucleus at the centre. This is in addition to the
Bohr's circular orbit.
2. Only those elliptical orbits are allowed for which each phase integral in phase space is
integral multiple of T in a complete period.
3. The velocity of electrons in elliptical orbits is not same at all points on the orbit. Thus there
is relativistic variation of mass with velocity at different points on the elliptical path.
Explanation of the model
According to this model
i) The motion of the electrons can be described with the help of two quantum numbers namely
radial quantum number n, and azimuthal quantum number np such that

ii)The variation of clectron velocity along the elliptical path changes the mass of the electron
according to the relativistic mass equation

17= which introduces a correction term to the Bohr's energy expression.

The correction term is given by

E'=--mZ'e* z'a2-2 and The total energy will be E, = E +E
E= 8e i?hn"
Success of the Model -_Explanation of the fine structure of spectralline
According to sommerfeld relativistic model, every ellipticai orbit corresponds to different
energy even though they have same quantum number.
If two quantum states are considered, then their energy levels must split into two levels. Transition
between the split levels must give rise to additional spectral lines. Hence the existence of fine
structure of spectral line can be explained partially..
LIMITATIONS OF THE MODEL
This model was not able to explain
. fully the fine structure of spectral lines.
11. The intensity of spectral lines.

critical potentials- Excitation and lonization potentials

Excitation potentials : It is the Minimum energy required to excite an electron from ground state to Excited

State

electron from the atom Or

lonization potentials : It is the Minimum energy required to remove an
electron from ground state to infinite excited state.
It is the Minimum energy required to move an

Franck and Hertz experiment - Determination of critical potentials

toward a positively charged grid in a glass tube filled with
Principle : Electrons are accelerated by a voltage with respect to the grid. A
a collection plate held at a small negative voltage
mercury vapor. Past the grid was
excited state can be found by accelerating
measure of the required for an electron to move to an
energy
where the ionic current through the grid is reduced.
voltage
Apparatus.

To Pump

(very nogative)
slightly
Hg vapor
nogative)
G P

V V2
A thermionic filament F , a grid G and a plate P is enclosed in a glass chamber as shown in figure 1. The
chamber is connected to a pump to regulate pressure inside the chamber. The distance between the grid and
plate should be less than the mean free path of electrons.
A small Pd is applied between the filament and the grid to accelerate the emitted electrons and the resultant
current is measured using an voltmeter V1. A small retarding potential V, is applied between G &P such that
V,< V1.Thus only those electrons having KE greater than the Pd (V2Vi) will go from G to P.
Procedure
Keeping Va constant, V is increased gradually in smail steps from Zero upwards. For each value the Plate current is
noted. A graph representing the plate current against the voltage V, is drawn. The resulting Curve is as shown in the
figure 2.

-4.9-
Ch» hC -(6 63 xIe)(3xic)
-4.9 2536 XIuO
.9
V

10 15
Accelerating Potenrial V1
Fig 2: Typlcal cnrve record ed in Franck Hertz
experim ent
Explanation of the result.
When the accelerating potential is increased gradually, elastic collisions occur between electrons and
mercury atoms between the Filament & grid G, without significant energy transfer to the mercury atoms
therefore the electrons will overcome the retarding potential& reach P.
On further increase of the accelerating voltage V, =V, the electrons lose their kinetic energy by making
inelastic colisions and can no longer reach the collector. The energy lost by the electron is gained by the
atom. Thus, the current reading given by the measuring amplifier decreases.

When the accelerating voltage is increased further, the kinetic energy of electrons increases to reach
the plate P. until their kinetic energy has become so large they are braked by a second non-elastic collision
with a mercury atom. This energy transfer recurs periodically with an increasing accelerating voltage. This is
shown as dip and peak in the resulting graph.
This periodic energy transfer is indicated by the recurrent and equidistant maxima and minima of the
collector electrode current as a function of the accelerating voltage. The minima are spaced at intervals of
4.9V, showing that the excitation energy of the mercury atoms is 4.9eV.

(In 1914, James Franck and Gustav Hertz performed an experiment which demonstrated the existence of excited states
in mercury atoms, helping to confirm the quantum theory which predicted that electrons occupied only discrete,
quantized energy states. Hence This experiment is a direct evidence for the quantised nature of energy levels in atoms.)\
VECTORATOM MODEL
characterizes
model. The new concepts that
This model is an extension of Bohr- Sommerfeld
the this model are
The concept of spatial quantization
of direction ( orientation of orbits)
1
Electron.
i. The concept of spinning

of direction:
The concept of spatial quantization size and shape). In
the magnitude of the orbit (both
The Bohr Sommerfeld model quantized
-

both magnitude and

vector atom model the
orientation of the orbits are also quantized. ie,
direction are quantized. This makes
the orbit a vector quantity.

directions w.r.t the

of electron can not be in all
Accordingly the planes of the orbits the angle between the
in certain discrete orientation. If 0 is
preferred direction but can only be then 0 can take only
direction perpendicular to the orbit plane,
preferred direction and the
the presence of external magnetic field.
certain values. This is possible only in

Concept of spinning electron

electron
proposed by Ulhenbeck and
Goudsmit. According to them the
This concept was
axis. Hence
orbit round the nucleus but also about
its own
revolves not only in an
in a solar system.This spin
electron is compared to the motion of planet
a
the motion of the
motion is also quantized.

Thus an electron has two angular momenta namely

. Orbital angular momentum and
Spin angular momentum

number 'S' has to be introduced to

Hence additional quantum number called spin quantum
an
rise
motion of electron constitutes electric current, giving
explain the electron motion. As the orbital magnetic
to magnetic field, an electron will
have two magnetic moments namely
moment will be the sum of orbital and
moment. The total magnetic
moment and Spin magnetic
Spin magnetic moments.
As both orbital and spin motion are quantized in
direction. They can be considered as
model.
such consideration is called Vector atom
quantized vectors. The model built on is provided by the
Note: The Evidence for the Spin and Spatial quantization
Stern and Gerlach experiment.

lines.
Explanation of Fine Structure of spectral
between two energy levels It is found the certain
A Spectral line arise due to transition electron
arises due to transition between same two
lines contain closely spaced lines ,which lines.
of lines are called Fine structure of spectral
energy states. These group
on the basis of electron spin.
The origin of fine structure of spectral
line is explained
motion and spin motion, both giving rise to separate
An electron will have both orbital
and momentum (s).The motion of electron in
spin
angular momentum ( 1)
The spin magnetic moment(4,) of the
the orbit produces magnetic field(B).
a
additional energy for the
SCose
electron interacts with this field resulting in
electron. This additional energy will be

3
 AE = - J s . B . Cos0 But
s (eh/2n m )s
AE =-
(eh B/27m). (s Cos0)
Buts Cose is the projection of s vector on the direction field B. Hence it has only two
values +1/2 or -1/2.Therefore ---
AE =
+(eh B /4Tm)
E AE Thus the energy levels will be split into two levels E + AE and E-
E AE. Transition between these two levels with the other energy levels
- E - AE produces closely spaced spectral lines called fine structure of spectral line.
As an
example consider the explanation of fine structure of sodium:
1 J=3/2 Sodium has one free electron in the outermost orbit. The
spectral lines are due to transition between P level and S
P level. For the upper P level, l= 1:J =3/2 or % For the
I=1 J 1/2 . lower S level , l = 0: J = %.
Applying the selection rule Altl and Aj=t1 or 0, two
DA D2 transitions (Di and D,)can be obtained. This explains the
fine structure of sodium D lines. On similar lines fine
I=0 J= 112 S structure of other spectral line can be
vector atom model is able to explained. Hence
explain the fine structure of spectral lines.

QUANTUM NUMBERS Associated with Vector atom model (& its significance)
According to Vector atom model , the following 7 quantum numbers are identified

1) Principle quantum number: (n) It determines the size of

the orbit and determines the total
energy of an electron in that orbit. It takes integral values like 1,2, 3, 4,....
2) Orbital quantum numbcr: (1). This specifies the mechanical
electron by the value lh/2t .I t determines the
angular momentum of the
shape of the orbit For a given value of °T can
.

take an integral value from 0 to (n-1) in

steps of unity.
3) Orbital magnetic quantum number (m1). This specifies the orientation
an external magnetic field. It is equal to of electron orbit in
projection of T' vector on the field direction .It can
take values from -l to +1 in steps
of unity. ie., a total of (21+1 )values.
4) Spin quantum number(s) .This specifies the mechanical spin angular momentum of
electronby the value sh/2 n.'s' has a value .
5) Spin magnetic quantum number(m,). This specifies the orientation of
electron in an external magnetic field.It is the spin momentum of
projection of I vector on the field direction. It
may be either parallel or anti parallel to the field and its value is either +1/2 or -1/2.
6) Total angular quantum number G). This refers to the resultant angular momentum of
electron due to both orbital and spin motions. It is
numerically equal to vector sum of l' and
's ie., j=l+s
j' is always a half integer.
7) Total magnetic quantum number (m) .It is the projection of j° vector on the external
mag. Field direction. It takes values from -j' to +j' excluding zero in steps of
Unity.
NOTE: The state of an electron in an atom can be completely specified by only four quantum
numbers namely n, l ,mi, m,
STERN-GERLACH EXPERIMENI
The aim of this experiment is to verify a) Concept of space quantization and b) Veify the
existence of electron spin.

Principle: The magnetic moment of an atom arises because the atom is considered as a tiny magnet.
In the presence of the external magnetic field, atoms experience a torque tending to rotate the
angular momentum& magnetic momentum vectors.

If field is uniform, this torque will be zero resulting in unaltered path of electrons. If the field is non-
uniform, the net torque on the atom will not be zero resulting in deviation of the electron path due
to additional force. This force is measured by Stern -Gerlach experiment.

Description of the apparatus.

Oven
Slit-1 Slit-2

Figure-1
Magnet
H P
Cross section of mag field.

Figure-2

The apparatus consists of an oven in which Silver atoms emerge through a horizontal slit.
Slits 1 and 2 defines a narrow beam of Silver as shown in figure -1.N and S are pole pieces of a
magnet which produces an inhomogeneous magnetic field. The pole pieces are shaped such that
one is Knife edged and the other is channeled as shown in figure-2. The entire apparatus is housed
in an evacuated chamber to avoid deflection silver atoms by gas molecules.

Procedure.

Without magnetic field, the silver beam is allowed to pass through slits 182 and then on to the plate
Pso that its trace is recorded. Then the magnetic field is switched on and the silver beam is allowed
to pass through slits on to the plate P through the inhomogeneous mag field. Its trace is recorded,on
the plate P.

Results of the experiment.

Without field with field

Fig-3a Fig- Sc
Fig-3

In the absence of Mag field, Silver atoms trace a sharp line as shown in fig. 3a. When inhomogeneous
mag field is applied, a double trace is obtained as shown in fig 3b. The convergence of two lines at
the top and bottom is due to the fact that field gradient decreases transversly. Different elements

aane difern pes d ace

 Double trace was
given by 2Cu, 70Au, gLi, 11Na, 19K& H2 In these elements, the
outer most electron was
's' electron with l=0 and j=t %. Hence = t1 Bohr magneton.
Three traces was
givenby the elements Ni, Co, Fe. Out of the three traces one was
in the undeviated present
position which means, some atoms have
u 0 and some have >1. =

Undeviated trace was given the

by elements 30Zn, asCd, 8oHg, soSn, s2Pb. In these elements.
There are no
unpaired electrons. Hence u= 0 for such atoms.
Discussion of results:

a) verification of
Spatial quantization: In external mag. field, silver atoms can take only
two possible orientations corresponding to s
two as
+1/2 =
and s= -1/2. Hence the beam splits into
shown in fig 3b.

According to classical theory j vector can take all

broad, continuous and diffused
possible orientations which should give
trace for silver as shown in fig 3c.
The very fact that this is not
obtained concludes that orientation of
This establishes the j vector are
quantized.
validity spatial
of
quantization
NOTE: The permitted orientations of J vectors are (2J+1). Hence only (2J+1) traces should be
obtained.

For one electron system l=0, s=1/2 and %

j=
Number of orientations =
no. of traces (2J+1)
=
2

For many electron systems, if l=0, s=1/2.

3/2. 5/2 etc and j= s

These conclusions were verified

by the experiment.
This establishes the
validity of spatial quantization.
b) Verification of concept of
spinning electron: For an electron, If the mag. Moment is
due to spin -orbit
coupling, then H cannot take all possible orientations. From the Hy
experiment the mag moment of Silver atom can be determined
between the two traces. The value so by the maximum separation
obtained was approximately 1 Bhor
magneton.
If spin absent, then for silver atoms J=0. & l=0,
was

that double trace is obtained shows

resulting in only one trace. The very fact
that vector j is only due to the spin of the electron. This
verifies the concept of electron
spin.
Iheory of Stern-Gerlach experiment lexpression fordeviationin the path ofatoms
P(BO ICos )
-

M
PB

X
B ICose Mag ield
aX

Consider an inhomogeneous magnetic field along X direction such that the field gradient dB
/dx is positive . let an atomic magnet MN of length I with pole strength P and magnetic moment M
be placed in this inhomogeneous magnetic field as shown in the figure.

Field strength at M = PB (acting along-X)

Field strength at N =
P(B+ ICos ) (acting along x )
dx

These two fields give rise to forces at M &N. These two forces constitute a couple producing a

translator effect on the atom due to the extra force p l c o s

dB where u= Pl = magnetic moment of the atom.

Translatoryforce Fx= p!cos= cOs
"dx
Due to translatory force the acceleration acquired by the atom x m

Due to the acceleration the displacement of t h e atom along the field direction is = D =

D-x2 2 m

D 14cos&
2
dB,2
dX m

distance Lin time t

When the atom enters the magneticfield let its velocity be V.If it travelsa
then t L/N. Therefore

resolved component
D-cos0 dBL or D=L4dB(L Where = 4, cosO is the
dX V) 2m d r )
of magnetic moment along field direction.
then
From the Kinetic theory of gases If T is the absolute temperature of the atom in gaseous state,

mKT
Therefore D=lu dB L2
2 m dX 3KT
 V sem Common paper-2
Atomic spectra

Angular moment of electron:

Orbital angular momentum. An electron moving in an orbit

possesses angular velocity which is a vector perpendicular to plane of
the orbit. Thus electron will possess an angular momentum called
orbital angular momentum. This is given by P = n°h = lh

Here I is an integer and I =0,1,2,3,4, ..(n-1).

Spin angular momentum: The electron moving in an orbit is also
associated with spinning motion about its own axis. This results in spin
angular momentum in addition to orbital angular momentum. The spin
angular momentum is a vector and is given by

Pssh=+ because s ==t%

Thus P, is also quantised.

ii. Total angular momentum: The vector addition of orbital angular momentum and spin angular
momentum of electron gives a new quantity called total angular momentum P,It is numerically
equal to sum of Pa and P.
P Pp+P, = lh + sh = (1+s)h = jh
Where j= I+s
The direction of j depends on direction of l and s.
If land s are parallel to each other then j =( l+s) represented by the vectors as

If l and s are anti parallel to each otherthen j = (- s) represented bythe vectors as

The possible values ofj are

J=+1/2 or j=1-1/2
Ifl =0, thenj = % only

If I=1 thenj =% or 3/2

Ifl=2 then j = 3/2 or 5/2
etc.,

Magnetic moment of electron:

Magnetic property is shown whenever an electron moves along a closed loop. In an atom, the orbital and
spin motion of electron is equivalent to flow of current though not confined in a wire.

This gives rise to two types of magnetic moments namely

1. Orbital magnetic moment

2. Spin magnetic moment
 V sem Common paper-3

is the
Expression for Orbitalmagneticmoment (u): Orbital magnetic moment
magneticmoment associated with orbital motion of electron. Let an electron of
mass m charge -e, move with a velocity in a Bohr orbit of radius r. This movement in

a loop constitutes a current i. The magnitude of the current is

i-0 Figure 1

Here T is the period of orbiting electron.

According to electromagnetic theory, a current loop produces

a magnetic field having magnetic
area of the loop.
moment as =iXA.(2) where A is the
Area of the loop is calculated using the figure 1

From the figure

T1
Area ofloop = A =[base X height

Height UV =OU X do = r dÙ, Base =

OY =r

Area of loop = A: odt (=dÙ/dt)

Integrating

A=oT.3)
Therefore equation (3) becomes
Ifangular momentum is P, then P =mr w.

Also P= lh.
m

Hence A = 1IhT. ()
2m
From equations 1, 2 and 4

-iXA T =eh
A-iXA T2 m 47Tm

eh
A - l is the expression for magentic moment
47tm
eh
is called Bohr magneton
T4 atomic and sub atomic magnetic
magnetic moment to measure
Bohr magneton: It is the smallest unit of
moments.
 SELECTION RULES
devised which govern the
satisfy the experimental observations certain principles
To are

transition between any two energy states to obtain a spectral line. These principles are called

selection rules. They are as follows

a) Selection rule for T (Al=t1).A spectral line will appear for which T value changes by t1.
D Selection rule for ' s " ( As =0).A spectral line will a p p e a r for which ' s ' v a l u e c h a n g e s b y 0.

ethe energy states having different 's do not combine.(transition must have same
multiplicity)
Selection rule for (Aj=t1 or 0).A spectral line will appear for whichj' value changes by ti
or 0.but
j=0 to j=0 transition is excluded.
d) Selection rule for'm
(Am=tl or 0).A spectral line will appear for which 'mj value changes
by t1 or 0.ie., either m,-0 or Am= t1
0,
COUPLING SCHEMES FOR MULTIELECTRON SYSTEM
In an
atom,different vectors (both orbital and spin ) may combine to give a new vector to
representthe atom .this combination depends on coupling between
there are two
types of coupling namely components of vectors .Hence
GL-S Coupling (i) J-J Coupling.
L-S Coupling
This is the
normally occurring coupling scheme. In this
momentum vectors of various electrons combine to forma type several orbital angular
momentum vectors of various resultant 'L' vector .several spin
electrons combine to form a angular
combine to form the vector T resultant 'S' vector. Then L' and
which represents the total 'S
scheme is possible only when
the interaction between
angular momentum of the atom. This
angular momentum of individual electrons are spins of individual electrons and orbital
L=h+lh+ la+ lat =Z strong. This scheme may be
(Lcan take (21 +1) represented as follows
orientations
in an external field.)
S S1+ S2+Sg+ S1 t =Zsi (S can take
(2s +1) orientations in an external field.)
Then J=L+S

can take (2J+1) orientations in an external field.

All the vectors
L,S,J are
quantized.
If S thenJ will have 2S+1 values
If LeS thenJ will
have 21+1 values
If L=S then J will have
S values

JCoupling
This coupling occurs when
the interaction between
than that between either orbital and spin vectors in
orbital vector or electrons is stronger
total angular momentum spin vector. The orbital and
spin
j' for the electron ,then the vectors add up to
j vectors of each electron add give
total angular momentum J
of the atom. up to give the

This scheme is
represented as follows,
il +S1, iz=lh +S2, is=ls tS3, ja=l4 +54,
-etc., Then J= J +J2 +Ja+Jat- -etc.,
Jcan take (2.J+1) oricntations in an external field.
All the vectors LS.J are quantized.
If L>S then J will have 2S+1 values
If L<S then J will have 2L+1 values
If L=S then J will have S values

-JCoupling in electrons isS

Tlis coupling when the interaction between orbital and spin vectors
occurs
vectors add
suunger than that between
either orbital vector or spin vector. The orbital and spin
add
for the electron ,then the "j' vectors of each electron
up to give total angular momentum j'
momentum J of the atom.
up to give the total angular
This scheme is represented as follows,
--etc., Then
+s jz=lh +s2, j3=ls +S3, j4=l4 +s4,
- - -

j J=Jj +J2 +J3+J4t--- -----etc.,

PAULT'S EXCLUSION PRINIPLE
all the four numbers same.
STATEMENT: No two electrons in an atom can have quantum
electron in an atom must have
EXPLANATION: According to Pauli's principle ,every
1, m, ms If any two electrons have
different set of quantum numbers. ie .,different set of n,
identical value of quantum number then one of them will be ,
excluded from entering into the
constitution of the atom Hence the name exclusion principle.

APPLICATION OF PAULT'S PRINCIPLE

) Determinationof Max number of electrons in an orbitor shell
there different subshells defined by 'T.
For a given value of'n'(shell) are

Max number of electrons in a shell = sum of max number of electrons in a sub shell
n-1
2 . (21+1) (factor 2 corresponds to Spin)
=0
2 [1+3 +5 ----=--------|

2 [sum of AP 1+3+5+.. .tlast term.]

= 2 [ " (2 +(n-1) 2}1
= 2 [n. {1+ (n-1)}1

Max number of electrons in a shell

=2[=2n ns
n= 1. the shell will have a max of 2 clectrons
n-2, the shell will have a max of 8 electrons
n- 3, the shell will have a max of 18electrons
n=4, the shell will have a max of 32 electrons
2) Valence electron and Pauli's principle. (Arrangement of electrons in periodic table)
Pauli's principle explains the scheme of successive formation of atoms as arranged in
the periodic table. Such arrangement requires different sets of quantum numbers for each
electron. The periodic table contains seven rows called periods and eight columns called
groups.
 Use of Pauli's
principle in finding the elctron conliguration of all the elements in
group nunber of unpaired clectrons
same a
(valence clectrons) for them. Hence, all the
belonging to a group have samne chemical elements
physical properties depend only on the valence properties, which show that the chemical and
Elements with same valenee electrons electrons.
presence of periods in the classification of largely possess similar properties that explain the
In the elements.
periodic table. a new
occupied afier the inner shells are period characterizes a new shell. This new shell will be
present in these new shells, which willcompletely filled. Hence., the valence electrons will be
3)Determination of electronic characterize he property of the element.
configuration
distribution of electrons in various of atoms Electronic configuration is the
atomic sub
lowest possible shells
energy sub shell. Every sub shell T according to the availability of
Hence the distribution of max will have a max of 2n* electrons.
electron in different sub shell
ISas shown according to pauli principle
Name
of the Max Max
(Shell) Sub m electrons electrons
shell (H to +1) ms in sub
a
in a shell
shell 2n
2.(21+1)
+1/2,-1/2
-1 ,0,+1 +1/2,-1/2
0
0
+1/2,-1/2 8
3 +1/2, -1/2
-1.0,+1 +1/2,-1/2 6 18
S
2,-10,+1.+2 1/2, -1/2 10
P
+1/2,-i/2
d
-1,0,+1 +1/2, -1/2 6
2.-1 .0.+1,+2 +1/2,-1/2 10 2
f -3,-2,-1 .0.+1,+2,+3+1/2,-1/2
Electrons having same 14
occupy same atomic Principle quantum number n will have same
sheilrepresented
having a certain value °T. In by K,M,N,L, ...etc. Each energy and
shell is divided into
a
given sub shell, all sub shell
of electrons in various subelectrons
The will have almost same
d 'f' (=0
occupancy energy.
,J=1, 1=2 ,l=3). shells is
symbols. The super script Each sub shell is identified byrepresented by the notation 'sp
its 'n'
Example 1S 2S 2P° 3S 3p on the sub shell followed
symbol gives the number of electrons by its sub shell
.etc., in that shell
The order of filling up of
1s 2s 2p° 3S electron in sub shell is
3P 4S 3d 4p 5s 4d0 given by
Examples of 5p 6S 4f sd 6P 7S
'Na :1S 2Selectronic2P° 3S'configuration 6d0..etc.
24Cr1s 2s2 2P 3S 3P 4S 3d
29Cu 1S 2s 2P 3s? (half filled 'd'
3P 4s 3d (fully filled 'd subshel)
n1s 2s 2p° 3S 3P° 4S 3d 'subshell)
Ag1S 2s 2P 3S
9 Au:1s 2s 2P 3S 3P 4S 3d0 4P 5s' 4d
3P 4S 3d 4P° 5S 4d Sp 6S' 4f" 5d
(fully filled f)