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UNIT III

DRAWBACKS OF BOHR AND SOMMERFELD ATOM MODEL:

1) Bohr’s atom model fails to explain fine structure of spectral lines even in the simplest
hydrogen atom.
2) Bohr’s atom model fails to calculate the energy of the system and frequencies of radiation
emitted in case of complex atoms.
3) Sommerfeld’s modification in Bohr’s atom model gave the theoretical explanation of fine
structure of spectral lines but it could not predict the correct number of fine lines.
4) Bohr and Sommerfeld atom model could not explain the distribution and arrangement of
electrons in atoms.
5) Bohr and Sommerfeld atom model could not explain the intensity distribution of spectral
lines.
6) Bohr and Sommerfeld atom model could not explain the anamolous Zeeman effect and
Stark effect.

VECTOR ATOM MODEL:

To overcome the limitations of Bohr and Sommerfeld atom model, Uhlenbeck and Goudsmit
proposed the new model known as vector atom model. It is the extension of Bohr and
Sommerfeld atom model. It is based on two important features

1) Space quantization;
2) Spinning of electron.

1) Space Quantization:

According to Bohr – Sommerfeld atom model the electron orbits are quantized with respect their
magnitudes i.e, size and shape. But there is no restriction on the orientations of orbits in the space. i.e, it
can orient in all possible directions in the space. Hence the orbital angular momentum L can take any
arbitrary direction in the space. The vector atom model extends the concept of quantization to the
orientations of the electron orbits in the space. According to this concept the electron orbits can orient
only in certain directions out of infinite possible orientations. Hence the orbital angular momentum L can
take only certain directions out of infinite possible directions in the space. This is known as space
quantization.

To specify the orientations of the electron orbits in the space, it is placed in the magnetic field and its
orientations are determined relative to the direction of magnetic field (Z – direction). The space
quantization of an electron orbit is specified by the projection of its orbital angular momentum L on to the
direction of magnetic field.

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2) Spinning of Electron:

The investigation of alkali metal spectra with help of high resolving power spectroscope shows that each
line of these spectra is doublet. For example the yellow line of sodium atom consists of two lines D 1 and
D2 with wave lengths 5896A0 and 5890A0 respectively. The Bohr – Summerfeld atom model could not
explain such fine structure of spectral lines.

In order to explain fine structure of spectral lines Uhlenbeck and Goudsmith proposed the concept of
spinning of electron. According to this concept electron revolves about its own axis, similar to the
spinning of the planets in the solar system.
The spin angular momentum of the electron is given by
h
ps 2  s , s is called spin quantum number and it has the value ½.
Quantum Numbers
The quantum numbers associated with each of the electrons in a given atom are given below:
a) The principle or total quantum number ‘n’ : The Principle quantum number (n)
defines the principle orbit (shell) for an electron. It can have only non-zero positive
integral values, that is n=1, 2, 3 , ……… The number of electrons in a shell is limited to
2n2. The energy levels or shells of electrons correspond to values of ‘n’ are as follow:

‘n’ values shell no. of electrons

1 K 2
2 L 8
3 M 18
.
.
Principle quantum number ‘n’ determines the energy of electron and its distance (radius
of the orbit) from the nucleus. The electron with n=1 is more near to the nucleus and is
having more potential energy than electron with n=2 and so on.
b) Orbital quantum number ‘l’ : The orbital quantum number (l) appears in the expression
for orbital angular momentum pl of the electron. It defines the shape of the orbital
occupied by the electron and orbital angular momentum of the electron. It can have any
integral values from 0 to (n-1). Each value of ‘l’ refers to a sub-shell or an orbital and
total number of orbitals in a shell is equal to the value of principle quantum number ‘n’.
The orbital quantum number ‘l’ thus can takes values l = 0,1,2,3,4,……, (n-
1) . The number of electrons in a sub-shell or in an orbital is limited to 2(2l+1). The
energy levels or sub-shells of electrons correspond to values of ‘l’ for given value of ‘n’
are as follow:

‘n’ values possible ‘l’ values 0 to (n-1) sub-shell no.of electrons 2(2l+1)
1 0 s 2
2 0 s 2
1 p 6
3 0 s 2
1 p 6
2 d 10
4 0 s 2
1 p 6
2 d 10
3 f 14
.
.

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c) Spin quantum number ‘s’ : The spin quantum number (s) appears in the expression for
spin angular momentum ps of the electron. It has been introduce to account for the spin of
the electron about its own axis. Since the electron can spins clockwise or anticlockwise,
there are two values given to ‘s’ as +1/2 and – 1/2 . Two electrons with same sign of spin
quantum number are said to have parallel spin and those having opposite sign of spin
quantum number are said to have anti-parallel spin.
d) Total quantum number ‘j’ : The total quantum number (j) appears in the expression for
resultant (total) angular momentum pj of the electron. Its numerical value is the vector
sum of ‘l’ and ‘s’ . It is usually expressed as j=l ± s where plus sign is used when electron
is having parallel spin and minus sign is used when electron is having anti-parallel spin.
e) Magnetic orbital quantum number ‘ml’ : When an atom is placed in strong magnetic
field H then according to space quantization ‘l’ can have limited orientation with
direction of magnetic field H. As shown in figure 2, the integral values of projection of ‘l’
along field direction are known as magnetic orbital quantum number ml. The permitted
values of ml are from +l to –l . Thus for each value of l there will be (2l+1) possible
values of ml .

Figure 2
f) Magnetic spin quantum number ms : Like magnetic orbital quantum number,
magnetic spin quantum number is the projection of spin vector on the field direction. The
permitted values of ms are from +1/2 and –1/2 .
g) Magnetic total quantum number mj : The values of this quantum number is the
projection of total quantum number vector ‘j’ along the field direction. Since ‘j’ can have
half integral values , mj can also have half integral values. . The permitted values of mj
are from +j to –j . Thus for each value of j there will be (2j+1) possible values of mj .
That is when an atom is placed in strong magnetic field each electron energy
level split into (2j+1) sub levels. This explains the splitting of spectral line in strong
magnetic field.

STERN – GERLACH EXPERIMENT:

Stern – Gerlach experiment gives the experimental proof of the important features of vector atom model.

Principle:

The atom is considered as small elementary magnet. Its magnetism is due to spin and orbital motion of
electrons. When this atomic magnet is placed in the uniform magnetic field, the two poles of the atomic
magnet will experience equal and opposite force. So it gets align along the field direction. But when this
atomic magnet is placed in non uniform magnetic field, the magnet not only aligns along field direction
but also experience translatory force.

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Experimental arrangement:

The experimental arrangement of S-G experiment is as shown in fig 1. The substance under investigation
is heated in an electrical oven O. The substance on heating emits the atomic rays in all possible directions
with velocity depending upon temperature of the substance.

The sharp atomic beam is allowed to pass through

non uniform magnetic field. The non uniform
magnetic field is obtained by using electromagnet
with specially constructed pole pieces (fig 2) and
sharp atomic beam is obtained by using slits S1 and
S2. The atomic beam is then allowed to strike on
photographic plate P, which records the path of the
beam. The magnetic field is made as intense and as
non uniform as possible.

Theory:

Suppose that the atomic magnet AB of pole strength p and effective length l is placed in non uniform
dH
magnetic field by making an angle  with x-axis as shown in figure. Let field has gradient dx along
positive direction of X-axis.
If the field strength at the end A of the magnet is H then at the other
dH
end B it will be H  l cos dx .
Therefore the magnetude of force at pole A is pH and the
dH
magnetude of force at pole B is p ( H  l cos  dx ) .

dH
Thus pl cos dx is the additional force acts on the pole B along positive direction of x- axis. This
force is responsible for the deviation of the atomic magnets from the straight line path. This additional
force will give an acceleration to the atomic magnet of magnetude

pl cos dH
force dx
ax  
mass M

Where M is a mass of an atom.

Therefore the deviation of the atomic magnet is given by

pl cos dH
D  u t  1 a t2  1 dx t 2 …….. (1) (Here ux=0)
x x 2 x 2 M
Where, t is time taken by the atom to cover distance d in the normal direction of the field.

d
t  v
Using in equation (1), we have

dH
1 pl cos dx  d 2
Dx   
2 M v

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3kT
Where, v is the thermal velocity of the atoms is given by v  . Where, k is Boltzmann constant.
M

Substitute pl cos   is the resolved component of magnetic moment in the field direction.

1
dH
dx  d 2
 Dx   
2 M v

Result:

The traces obtained on the photographic plate in the case of Silver atom without and with field
are as shown in figure. The single trace is obtained with field and double trace is obtained with
field. By knowing the value of d, v, dH/dx and Dx the value of  can be calculated. The value
of magnetic moment of silver comes to be one Bohr magneton.

Proof Spin of electron:

In case of silver, the single trace of path splits into two lines, by the non-uniform magnetic field, showing
the value of  1. If we consider the ground state of silver atom and neglect the electron spin then L=0,
S=0 and J=0. Since J=0, mj can have (2J+1) values i.e, only one value (0). Hence magnetic moment
  m j g =0. (Where mj is total magnetic quantum number and g is Lande’s splitting factor).

But if we admit the existence of electron spin and give it a value ½, then J = ½, therefore mj can have
(2J+1) values i.e, two values ( 1 2 ). Hence   m j g will have two values i.e,  1 (since g = 2 for
spin motion). So the results obtained are complete agreement with theory.

Proof of Space quantization:

According to classical concept, the atomic magnets can orient themselves in all possible directions, and
then we should get diffuse trace on the photographic plate. But in actual we get two distinct traces in case
of silver atom. The two traces on the photographic plate can be explained if we consider the a space
quantization of spin angular momentum i.e, only certain orientation of spin angular momentum are
possible. For ground state of silver atom we have L=0 and S = ½ and then J = ½ . Therefore possible
orientations will be (2J+1) = 2. Hence we get only two distinct traces on the photographic plate.

COUPLING SCEMES:

Every electron in an atom has an orbital angular momentum and spin angular momentum. The orbital and
spin angular momenta of every electron adds up to form the resultant angular momentum of the atom.
There are mainly two ways in which the different vectors of electrons combine to give the resultant vector
for the atom as whole. They are known as L-S coupling and j-j coupling.

L-S Coupling:

In this coupling, all the orbital vectors (l) of the electrons combines to form a resultant orbital vector (L)
and all the spin (s) vectors of the electrons combines to form a resultant spin vector (S). Then the vectors
L and S combine to form the vector J which represents the total angular momentum of the atom.

L =l1 + l2+ l3 + l4 + …………, S =s1 + s2+ s3 + s4 + …………

And total angular momentum is J=L+S.

i) Orbital quantum numbers li are always integer. Hence L is always integer.

ii) Spin quantum numbers si are always half integer. Hence S is half integer for odd number
of electrons and integer for even number of electrons.
iii) Consequently, J will be integer if S is integer and half integer if S is half integer. The quantum
number J has one of the following values:
L+S, L+S-1, L+S-2,…..,L-S.

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j-j coupling:
In case of heavy atoms the interaction between orbital (l) and spin vectors (s) of individual electrons is
strong as compared to the interaction between spin-spin (s-s) or orbital-orbital (l-l) vectors of the different
electrons in an atom. Consequently, the l and s vectors of each electron first combine to form their
resultant j and then the j vectors of all the electrons combine to form resultant vector J of the atom. This
kind of coupling is called j-j coupling.

SELECTION RULES:

In an atom there are number of energy states. It is observed that all the electronic transitions between
different energy states (as spectral lines) do not occur. The electronic transitions governed by certain rules
known as selection rules. There are three selection rules

i) The selection rule for L: only those transitions are possible for which the value L is changes by
+1 or -1.

ii) The selection rule for S: only those transitions are possible for which the value S is changes 0.

iii) The selection rule for J: only those transitions are possible for which the value J is changes by
+1,-1or 0.

In presence of magnetic field, the selection rules are ml =+1,-1 or 0 and ms = 0

And mj = +1,-1 or 0.

INTENSITY RULES:

Whether a spectral line due to an allowed transition is weak or intense is determined by the intensity
rules. They are as follows:

1) A spectral line will be intense for which electron transition takes place in such way that L and J
change in the same sense.
2) A spectral line will be weak for which electron transition takes place in such way that L and J
change in the opposite sense.
3) A spectral line will be intense for which electron transition takes place in such way that L and J
decrease. i.e, L L – 1 and J J – 1.
4) A spectral line will be less intense for which electron transition takes place in such way that L and
J increase. i.e, L L + 1 and J J + 1.
5) The oppositely directed transitions do not occur. The above rules may be summerised as follows:

∆L = -1, ∆J = -1 Very intense

∆L = -1, ∆J = 0 less intense

∆L = +1, ∆J = +1 Weak

∆L = +1, ∆J = 0 Weak

∆L = -1, ∆J = +1 No transition

∆L = +1, ∆J = -1 No transition

ORIGIN OF X-RAYS:

When the fast moving electrons strike on the target element of high atomic number, then few number of
fast moving electrons lose their kinetic energy to target particles. This loss of kinetic energy is responsible
for the production of X-rays. The loss kinetic energy may takes place in two ways and accordingly we get
two types of X-ray spectrums.

1) Continuous X-ray spectrum;

2) Characterize X-ray spectrum.

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Origin Continuous X-ray spectrum:

The few fast moving electrons which strike the target penetrate deep into the atom of target element and
are attracted by the attractive forces of their nuclei. Due to these forces, the striking electrons get
deflected from their original paths. In this way electrons are de-accelerated, i.e, their velocity is reduced
and this gives rise to a loss of kinetic energy. The loss of kinetic energy during retardation is given off in
the form X-rays of continuously varying wave length. This is called as Continuous X-ray spectrum.

Features of Continuous X-ray spectrum:

The plots of intensity against the wave length of continuous X-rays from tungsten as a target, at different
accelerating potentials is shown in fig 1.

From the graph, we can say that

1) The wavelength at which maximum intensity occurs shifts to

lower values for higher accelerating potentials.
2) With increase in accelerating potential, the total intensity of X-
ray increases.
3) The radiation emitted has continuous wavelengths.
4) For any given accelerating potential, there is sharply defined
minimum wavelength, called short wavelength limit.
5) Duane and Hunt experimentally found that the short wavelength
limit is inversely proportional to the accelerating potential V. It is
given by
12400
min  V Ao
This relation is known as Duane and Hunt law. The short wave length limit at given accelerating
potential is independent on target element.

Origin of Characteristic X-ray spectrum:

The origin of characteristics X-ray spectrum was explained

on the basis of Bohr’s model of atom. According to this
model electrons in the atom are arranged into various shells
called K, L, M, N….. etc. An atom radiates energy when an
electron jumps from one stationary orbit to another
stationary orbit. Normally, electrons transitions cannot takes
place from the outermost orbits to the innermost orbits
because innermost orbits are occupied. Such transition can
occurs only when very high energy electron knock out an
inner core electron belonging to K,L,…shells. An electron
from an outer orbit jumps to fill up the vacancy in inner
orbit and the energy difference is emitted as X-rays. The
wave length of emitted X-rays is depends on the target
element. The X-ray spectra consists of series of sharp lines
and are characteristic of target element, hence it is known as
characteristic X-ray spectra.

The group of lines having shortest wavelength is called K-series. These lines occurs when an electron
from the K-shell is knocked out and the resultant vacancy is filled by an electron from the next higher
shell L,M,…etc. If an electron from L-shell jumps to K-shell the energy difference (EL-EK) is emitted in
the form of K radiation. If an electron from M-shell jumps to K-shell the energy difference (EM-EK) is
emitted in the form of K radiation. In similar way the L-series ( L , L ,...etc ) is produced when
vacancies in L-shell are filled by an electron from the next higher shell M,N,…etc.

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Moseley’s Law:

The British physicist Henry Moseley carried out the systematic investigations on the characteristics X-ray
spectra from various target elements. He found that different target elements produce similar spectra
consisting of K, L and M series. He measured the wavelengths of X-ray spectra from various targets by
using Bragg’s spectrometer. He found that frequencies of these rays depend on the atomic number of the
target element by the following mathematical relationship

a(Z)ora2(Z)2

Where a and  are the constants.

This relationship is known as Moseley Law. It states that the

frequency of spectral line in the characteristic X-ray
spectrum varies directly as the square of atomic number Z of
the element emitting it.

The plot drawn between square root of frequency of X-ray

line and atomic no. of the target element is a straight line for
each series, as shown in figure. Such plot is called Moseley
plot.

The values of the constants a and  are determined by the

slope and intercept of the straight line.

The constant  is called screening constant. For K-series  =1.

Derivation of Moseley’s Law:

The Moseley’s law can be explained on the basis of Bohr’s theory. Let us consider an atom of large
atomic number Z. The energy of an electron in an atom is given by

m ( Ze ) 2 e2  1 
En  2 2  2
h
8 0
n 
Where, (Ze) is the nuclear charge. Accordingly, the energies of electron in an orbit of principle quantum
number n1 and n2 can be written as

E m( Ze) 2 e2  1 
n1 
2 2  2 …………… (1)
h n
8 0  1
E m( Ze ) e  1 
2 2
n2  2 2  2 …………… (2)
n
8 0 h  2 
Taking into account the screening effect due to electrons, the positive charge of the nucleus, seen by the
electron under consideration, reduces to ( Z  ) from Z.

E m( Z  )2 e4  1 
  2  ………. (3)
1
n1
2 2

h n
8 0  1
&E m( Z  2 ) e  1 
2 4
n2  2 2  2 ………. (4)
h n
8 0  2 
The difference in energy E  En  En is given by
2 1

me4  ( Z   ) 2 ( Z  2 )2 
E  22  2  2  1

8 0 h  n 1 n2 

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It may be taken as σ1= σ2= σ.

me4  1 1
E  2 2 ( Z   )2  2  2 
n
8 0 h  1 n2 
Therefore frequency of X-ray emitted in the transition is given by

 E
  h 
me4  1 1
 2 3 ( Z   ) 2
 2  2
h n
8 0  1 n2 
The K-series is due to transitions from higher states to n = 1 state. Therefore n1= 1.

me4 1 1
 2 3 ( Z   )2   2 
h
8 0 1 n2 
Or   a 2 ( Z  )2

This relationship is known as Moseley Law.

me4  1
Where, a  1
2
2 3  2

h n
8 0  2 

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