SWM PDF

Dr. Dr.
Vinod Vinod Patidar Patidar

Physi c s of Mat er i al s f or B. Tec h (ECE/CE/ME) I I Sem Physi c s of Mat er i al s f or B. Tec h (ECE/CE/ME) I I Sem
Si r Padampat Si nghani a Uni ver si t y, Udai pur
1 1 PH 103 PH 103
In classical mechanics
In classical mechanics
-
-
The future of a particle may be predicted with certainty
The future of a particle may be predicted with certainty
using the Newton's
using the Newton's
law if the force acting on the particle (or

law if the force acting on the particle (or
equivalently potential energy) and the initial position and
equivalently potential energy) and the initial position and
velocity are known.
velocity are known.
it is done by solving the second order differential equation F
it is done by solving the second order differential equation F
= ma . The solution of such equation describes the future of
= ma . The solution of such equation describes the future of
particle with certainty i.e. the trajectory of the particle .
particle with certainty i.e. the trajectory of the particle .
Similarly, Maxwell
Similarly, Maxwell
s (first order differential equations)

s (first order differential equations)
equations are used to find the electric and magnetic field
equations are used to find the electric and magnetic field
associated with any charge distribution. In this case also
associated with any charge distribution. In this case also
the solution of first order equations are required.
the solution of first order equations are required.
Quantum Mechanics
Quantum Mechanics
Dr. Dr. Vinod Vinod Patidar Patidar
2 2 PH 103 PH 103
Similarly in quantum mechanics, the basic equation to be
Similarly in quantum mechanics, the basic equation to be
solved to get information about the particle
solved to get information about the particle
s future is known
s future is known
as
as
Schr
Schr
dinger equation
dinger equation
.
.
Like the Newton
Like the Newton
s law it is also written for a certain value of

s law it is also written for a certain value of
force (or conveniently for the potential energy).
force (or conveniently for the potential energy).
Unlike the Newton
Unlike the Newton
s law, the
s law, the
Schr
Schr
dinger equation
dinger equation
does not
does not
give the trajectories of the particle, instead its solution give
give the trajectories of the particle, instead its solution give
s
s
the
the
wave function
wave function
of the particle, which carries the
of the particle, which carries the
information about the particle
information about the particle
s wave like
s wave like
behaviour
behaviour
.
.
3 3 PH 103 PH 103
Schr
Schr
dinger equation
dinger equation
Newton
Newton
s law / Maxwell
s law / Maxwell
s equations / Schr
s equations / Schr
dinger equation
dinger equation
can not be derived from basic principles. Instead they
can not be derived from basic principles. Instead they
should be regarded as equations written to agree with
should be regarded as equations written to agree with
previous experimental and theoretical results and to satisfy
previous experimental and theoretical results and to satisfy
certain symmetry and conservation principles.
certain symmetry and conservation principles.
The desired equation
The desired equation
1. must be consistent with conservation of energy i.e.
1. must be consistent with conservation of energy i.e.
E = K + U
E = K + U
2.
2.
must be consistent with the de
must be consistent with the de
Broglie
Broglie
hypothesis i.e. if
hypothesis i.e. if
we consider a free particle with momentum p, we must
we consider a free particle with momentum p, we must
obtain a wavelength
obtain a wavelength
m
p
K
2
2
=
p
h
=
4 4 PH 103 PH 103
Or equivalently the momentum
Or equivalently the momentum k
h
p h = =
m
k
K
2
2 2
h
=
3.
3.
must be well behaved in mathematical sense i.e. the
must be well behaved in mathematical sense i.e. the
solution must be continuous, single valued and the
solution must be continuous, single valued and the
governing equation should be linear (otherwise the
governing equation should be linear (otherwise the
superposition principle would not be applicable).
superposition principle would not be applicable).
Now we look for the equation, with above mentioned
Now we look for the equation, with above mentioned
properties
properties
i.e
i.e
having the solution as a free particle de
having the solution as a free particle de
Broglie
Broglie
wave.
wave.
We start with the solution i.e. equation of wave
We start with the solution i.e. equation of wave
propagating in x direction and wavelength
propagating in x direction and wavelength
5 5 PH 103 PH 103
) sin( ) , ( t kx A t x y =
k
2
= 2 =
To simplify the problem, we initially start with the time
To simplify the problem, we initially start with the time
independent solution i.e. we seek an equation with the
independent solution i.e. we seek an equation with the
following time independent solution
following time independent solution
The equation must involve the potential energy
The equation must involve the potential energy
U.
U.
If
If
U
U
appear in first power then the kinetic energy
appear in first power then the kinetic energy
K
K
must
must
appear in first power
appear in first power
) sin( ) ( kx A x =
= =
) (
1 ) (
2 2
2
2 2 2 2
x dx
x d
m m
k
K
h h
2
2 2
) (
2
) (
dx
x d
m
x K

h
=
6 6 PH 103 PH 103
) (
2 ) (
2 2
2
x K
m
dx
x d
h
=
U K E + =
since
since
) ( ) (
2 ) (
2 2
2
x U E
m
dx
x d
=
h
) ( ) (
) (
2
2
2 2
x E x U
dx
x d
m

= +
h
It is known as
It is known as
time independent one dimensional Schr
time independent one dimensional Schr
dinger equation
dinger equation
It is second order differential equation, which is
It is second order differential equation, which is
1. Consistent with energy conservation,
1. Consistent with energy conservation,
2. Has linear and single
2. Has linear and single
-
-
valued solution
valued solution
3, gives a free particle solution consistent with single de
3, gives a free particle solution consistent with single de
Broglie
Broglie
wave length
wave length
7 7 PH 103 PH 103
Wave function
Wave function
The goal in solving the Schr
The goal in solving the Schr
dinger equation is to obtain the

dinger equation is to obtain the
wave properties of particle. These properties can be
wave properties of particle. These properties can be
described by using the wave function
described by using the wave function
) (x
which represents a wave which consist a unique wavelength
which represents a wave which consist a unique wavelength
moving with certain phase velocity or a mixture of wavelength
moving with certain phase velocity or a mixture of wavelength
(wave group) moving with certain group velocity.
(wave group) moving with certain group velocity.
The square absolute amplitude gives the probability for
The square absolute amplitude gives the probability for
finding the particle at
finding the particle at
a given location in space i.e.
a given location in space i.e.
dx x dx x P
2
| ) ( | ) ( =
gives the probability of finding the particle
gives the probability of finding the particle
in the interval
in the interval
x
x
to
to
x+dx
x+dx
,
,
it is known as
it is known as
probability density.
probability density.
8 8 PH 103 PH 103
Boundary conditions
Boundary conditions
The represents the probability density, and the
The represents the probability density, and the
probability changes continuously like a well behaved wave
probability changes continuously like a well behaved wave
hence the
hence the
behaviour
behaviour
of should be continuous i.e.
of should be continuous i.e.
should be continuous and well behaved function.
should be continuous and well behaved function. ) (x
2
| ) ( | x
2
| ) ( | x
The can not be infinity.
The can not be infinity.
2
| ) ( | x
0 ) ( ; x x As
dx
x) (
should also be continuous
should also be continuous
as it represents the momentum.
as it represents the momentum.
The probability of finding the particle between two points
The probability of finding the particle between two points
x
x
1 1
and
and
x
x
2 2
is given by
is given by

=
2
1
2
1
2
| ) ( | ) (
x
x
x
x
dx x dx x P
9 9 PH 103 PH 103
If and then
If and then

= = 1 | ) ( | ) (
2
dx x dx x P

2
x

1
x
The above condition is known as
The above condition is known as
Normalization condition.
Normalization condition.
Average value or expectation value
Average value or expectation value
If we perform the measurement of the position or any other
If we perform the measurement of the position or any other
physical quantity that depends on position, we can not
physical quantity that depends on position, we can not
guarantee the outcome. Instead we can define the outcome
guarantee the outcome. Instead we can define the outcome
of the experiment in terms of probable or average value after
of the experiment in terms of probable or average value after
a large number of measurements.
a large number of measurements.
=
n
x n
x
i i
average
10 10 PH 103 PH 103
If the wave function is normalized
If the wave function is normalized
Similarly, the expectation value of any physical quantity
Similarly, the expectation value of any physical quantity
f(x
f(x
)
)
,
,
which depends on x is given by
which depends on x is given by

= =
dx x
xdx x
dx x P
dx x x P
x
average
2
2
| ) ( |
| ) ( |
) (
) (
> =< =

x xdx x x
average
2
| ) ( |
It is known as
It is known as
expectation value of x.
expectation value of x.

>= < dx x f x x f ) ( | ) ( | ) (
2

11 11 PH 103 PH 103
The Free particle
The Free particle
Free particle means the particle which is freely moving i.e.,
Free particle means the particle which is freely moving i.e.,
no force acting F= 0 or Potential energy (U) =constant. For
no force acting F= 0 or Potential energy (U) =constant. For
convenience we may choose constant =0. Now write the
convenience we may choose constant =0. Now write the
Schr
Schr
dinger equation with U=0

dinger equation with U=0
Applications of
Applications of
Schr
Schr
dinger Equation
dinger Equation
) (
) (
2
2
2 2
x E
dx
x d
m

=
h
) (
) (
2
2
2
x k
dx
x d
=
2
2
2
h
mE
k =
where
where
12 12 PH 103 PH 103
Since is always positive, so the solution of above second
Since is always positive, so the solution of above second
order differential equation will be
order differential equation will be
kx B kx A x cos sin ) ( + =
m
k
E
2
2 2
h
=
2
k
It is difficult to evaluate constants A and B using the
It is difficult to evaluate constants A and B using the
normalization and boundary conditions as x extends up to
normalization and boundary conditions as x extends up to
(+/
(+/
-
-
) infinity ,hence we will not be able to find probabilities
) infinity ,hence we will not be able to find probabilities
from the above wave function.
from the above wave function.
Particle in one
Particle in one
-
-
dimensional Box
dimensional Box
> <

=
L x x
L x
x U
& 0
0 0
) (
It is also known as
It is also known as
infinite potential well
infinite potential well
13 13 PH 103 PH 103
Now we write the Schr
Now we write the Schr
dinger equation separately for the

dinger equation separately for the
region inside and outside the box.
region inside and outside the box.
U
0 ) ( = x
If we use in the Schr
If we use in the Schr
dinger equation, the equation

dinger equation, the equation
becomes physically meaningless. To make it meaningful,
becomes physically meaningless. To make it meaningful,
we have to choose outside the potential box.
we have to choose outside the potential box.
We can consider as an example for this situation, a bead
We can consider as an example for this situation, a bead
sliding on a stretched wire between two rigid walls and
sliding on a stretched wire between two rigid walls and
exhibiting perfectly elastic collision with the walls. If the wa
exhibiting perfectly elastic collision with the walls. If the wa
ll
ll
are perfectly rigid then the particle must always remain in
are perfectly rigid then the particle must always remain in
the box i.e. probability of finding the particle outside the box
the box i.e. probability of finding the particle outside the box
must be zero.
must be zero.
) ( ) (
) (
2
2
2 2
x E x U
dx
x d
m

= +
h
L x x x > < = , 0 0 ) (
14 14 PH 103 PH 103
Schrodinger
Schrodinger
equation inside the potential box will be i.e. for
equation inside the potential box will be i.e. for
(U=0):
(U=0):
L x x E
dx
x d
m
= 0 ) (
) (
2
2
2 2
h
L x kx B kx A x + = 0 cos sin ) (
The solution will be:
The solution will be:
where
where
Now we evaluate, A and B using boundary conditions. From
Now we evaluate, A and B using boundary conditions. From
the continuity condition on at
the continuity condition on at
x=0
x=0
and
and
x=L.
x=L.
) (x
At x=0: i.e.
At x=0: i.e.
B=0
B=0
hence
hence
0 ) ( = x kx A x sin ) ( =
At x=L: i.e.
At x=L: i.e. 0 ) ( = x
0 sin ) ( = = kL A L
Either A=0 or i.e.
Either A=0 or i.e.
0 sin = kL
.... 2 , 1 = = n where n kL
2
2
2
h
mE
k =
15 15 PH 103 PH 103
What is the complete
What is the complete
wavefunction
wavefunction
?
?
.... 2 , 1
2
= = n where n L
mE
h
.... 2 , 1
2
2
2 2 2
= = n
mL
n
E
h
2
2 2
0
2mL
E
h
=
..... 9 , 4
0 2 0 1
E E E E = =
kx A x sin ) ( =

=1 | ) ( |
2
dx x
Using normalization condition
Using normalization condition

= = 1 sin sin
2 2 2 2
xdx
L
n
A kxdx A

L
A
2
=
The complete
The complete
wavefunction
wavefunction
... 3 , 2 , 1 sin
2
) ( = = n x
L
n
L
x


16 16 PH 103 PH 103
We can draw following conclusions from above analysis:
We can draw following conclusions from above analysis:
1. A trapped particle can not have an arbitrary energy, as a
1. A trapped particle can not have an arbitrary energy, as a
free particle can. Its confinement in certain region leads to
free particle can. Its confinement in certain region leads to
restrictions on its wave function that allow to have only
restrictions on its wave function that allow to have only
certain specific energies and not others. These energies
certain specific energies and not others. These energies
depend on the mass of the particle and region of
depend on the mass of the particle and region of
confinement.
confinement.
2. A trapped particle can not have zero energy, since the de
2. A trapped particle can not have zero energy, since the de
Broglie
Broglie
wavelength of the particle is if
wavelength of the particle is if
By no means a trapped particle can have infinite wavelength.
By no means a trapped particle can have infinite wavelength.
Hence kinetic energy can not be zero.
Hence kinetic energy can not be zero.
3. Quantization of energy is conspicuous only when m and L
3. Quantization of energy is conspicuous only when m and L
are so small. This is why we do not experience energy
are so small. This is why we do not experience energy
quantization with daily life objects.
quantization with daily life objects.
mv h / = = = 0 v
17 17 PH 103 PH 103
Particle in two
Particle in two
-
-
dimensional Box
dimensional Box
> < > <

=
L y y and L x x
L y L x
y x U
& 0 & 0
0 & 0 0
) , (
L y L x y x E
y
y x
x
y x
m
=
0 & 0 ) , (
) , ( ) , (
2
2
2
2
2 2
h
L y L x y g x f y x = 0 & 0 ) ( ) ( ) , (
y k D y k C y g
x k B x k A x f
y y
x x
sin sin ) (
cos sin ) (
+ =
+ =
After applying the boundary conditions and normalization conditi
After applying the boundary conditions and normalization conditi
ons
ons
.... 2 , 1 , ) (
2
2 2
2
2 2
= + =
y x y x
n n n n
mL
E
h
18 18 PH 103 PH 103
Degeneracy:
Degeneracy:
For two different sets of quantum numbers, if we have the same
For two different sets of quantum numbers, if we have the same
energy
energy
eigen
eigen
value, then this energy level is known degenerate
value, then this energy level is known degenerate
energy level.
energy level.
Similarly, for three
Similarly, for three
-
-
dimensional potential box
dimensional potential box
.... 2 , 1 , , ) (
2
2 2 2
2
2 2
= + + =
z y x z y x
n n n n n n
mL
E
h
z
L
n
L
y
L
n
L
x
L
n
L
x
z
y
x

sin
2
sin
2
sin
2
) ( =
19 19 PH 103 PH 103
Finite potential Step:
Finite potential Step:
0
U
) ( ) (
) (
2
2
2 2
x E x U
dx
x d
m

= +
h
>
=
0
0 0
) (
0
x U
x
x U
If we assume that the wave functions in regions (1) and (2)
If we assume that the wave functions in regions (1) and (2)
respectively denoted by and
respectively denoted by and
) (
1
x ) (
2
x
) (
) (
2
1
2
1
2 2
x E
dx
x d
m

=
h
) (
) (
1
2
1
2
1
2
x k
dx
x d
=
2
2
1
2
h
mE
k =
20 20 PH 103 PH 103
0 ) (
1 1
1 1 1
+ =

x e B e A x
x ik x ik
Here A
Here A
1 1
and A
and A
2 2
are constants.
are constants.
For region second, if we assume E<U
For region second, if we assume E<U
0 0
0 ) ( ) (
2 ) (
2 0
2 2
2
2
= x E U
m
dx
x d
h
2
0
2
2
) ( 2
h
E U m
k

=
) (
) (
2
2
2
2
2
2
x k
dx
x d
=
0 ) (
2 2
2 2 2
+ =

x e B e A x
x k x k
On applying the condition that the wave function must be finite

On applying the condition that the wave function must be finite
everywhere x>0 gives B
everywhere x>0 gives B
2 2
=0
=0
0 ) (
2
2 2
=

x e A x
x k

21 21 PH 103 PH 103
The wave function must be continuous at x=0
The wave function must be continuous at x=0
0 ) ( ) (
2 1
= = x at x x
2 1 1
A B A = +
The first derivate of the wave function must be continuous at x=
The first derivate of the wave function must be continuous at x=
0
0
0
) ( ) (
2 1
= = x at
dx
x
dx
x
2 2 1 1 1 1
A k B ik A ik =
Solve two equations for B
Solve two equations for B
1 1
and A
and A
2 2
in terms of A
in terms of A
1. 1.
) (
) 2 (
2
2
2
1
1
2
1 2 1
2
2
1
k k
A k k ik k
B
+
+
=
) (
) ( 2
2
2
2
1
1 2 1 1
2
k k
A ik k k
A
+
=
22 22 PH 103 PH 103
It is clear from the above expressions that A
It is clear from the above expressions that A
2 2
is not zero. Hence
is not zero. Hence
the probability density of the particle being found in the regio
the probability density of the particle being found in the regio
n II is
n II is
not equal to zero. This result implies that there is a finite
not equal to zero. This result implies that there is a finite
probability that the incident particle will penetrate the potent
probability that the incident particle will penetrate the potent
ial
ial
barrier and exist in region II. This penetration is not allowed
barrier and exist in region II. This penetration is not allowed
classically.
classically.
Finite Potential Barrier:
Finite Potential Barrier:
< <

=
L x U
L x x
x U
0
& 0 0
) (
0
If we assume that the wave functions in regions (1) , (2) and (3
If we assume that the wave functions in regions (1) , (2) and (3
)
)
are respectively denoted by , and
are respectively denoted by , and
) (
1
x ) (
2
x ) (
3
x
23 23 PH 103 PH 103
0 ) (
) (
2
1
2
1
2 2
= x x E
dx
x d
m

h
) (
) (
1
2
1
2
1
2
x k
dx
x d
=
Schr
Schr
dinger equation for region (1)

2
2
1
2
h
mE
k =
0 ) (
1 1
1 1 1
+ =

x e B e A x
x ik x ik
Schr
Schr

L x x E
dx
x d
m
= ) (
) (
2
3
2
3
2 2
h
) (
) (
3
2
1
2
3
2
x k
dx
x d
=
2
2
1
2
h
mE
k =
L x e B e A x
x ik x ik
+ =

1 1
3 3 3
) (
24 24 PH 103 PH 103
Schr
Schr
dinger equation for region (2) (if we also assume E<

dinger equation for region (2) (if we also assume E<
U
U
o o
)
)
0 ) ( ) (
2 ) (
2 0
2 2
2
2
= x E U
m
dx
x d
h
2
0
2
2
) ( 2
h
E U m
k

=
) (
) (
2
2
2
2
2
2
x k
dx
x d
=
L x e B e A x
x k x k
< < + =

0 ) (
2 2
2 2 2
Since there is no particle coming from right to left in the regi

Since there is no particle coming from right to left in the regi
on (3),
on (3),
hence the coefficient B
hence the coefficient B
3 3
=0.
=0.
L x e A x
x ik
=
1
3 3
) (
Now applying the boundary conditions at x=0 and x=L
Now applying the boundary conditions at x=0 and x=L
0 ) ( ) (
2 1
= = x at x x
L x at x x = = ) ( ) (
3 2

25 25 PH 103 PH 103
0
) ( ) (
2 1
= = x at
dx
x d
dx
x d
L x at
dx
x d
dx
x d
= =
) ( ) (
3 2

After applying the conditions, we get
After applying the conditions, we get
2 2 1 1
B A B A + = +
2 2 2 2 1 1 1 1
B k A k ik B ik A + =
L ik L k L k
e A e B e A
1 2 2
3 2 2
= +
L ik L k L k
e A ik e B k e A k
1 2 2
3 1 2 2 2 2
= +
On solving these equations for A
On solving these equations for A
1 1
and B
and B
1 1
in terms of A
in terms of A
3 3
, we get
, we get
L ik
e A L k
k
k
k
k i
L k A
1
3 2
2
1
1
2
2 1
sinh
2
cosh

+ =
L ik
e A L k
k
k
k
k i
B
1
3 2
2
1
1
2
1
sinh
2

+ =
26 26 PH 103 PH 103
Reflection coefficient:
Reflection coefficient:
L k
k
k
k
k
L k
L k
k
k
k
k
A A
B B
R
2
2
2
2
1
1
2
2
2
2
2
2
2
1
1
2
*
1 1
*
1 1
sinh
4
1
cosh
sinh
4
1
+
= =
On substituting values of k
On substituting values of k
1 1
and k
and k
2 2
L k
E U E
U
L k
E U E
U
R
2
2
0
2
0
2
2
0
2
0
sinh
) ( 4
1
sinh
) ( 4
=
Transmission coefficient:
Transmission coefficient:
L k
E U E
U A A
A A
T
2
2
0
2
0
*
1 1
*
3 3
sinh
) ( 4
1
1
+
= =
1 = +T R
27 27 PH 103 PH 103
Conclusions:
Conclusions:
1. 1.
The transmission coefficient is zero if E=0. It has a finite val
The transmission coefficient is zero if E=0. It has a finite val
ue
ue
less than 1 for an incident beam having nonzero kinetic energy.
less than 1 for an incident beam having nonzero kinetic energy.
i.e. there is a finite probability for a particle to tunnel thro
i.e. there is a finite probability for a particle to tunnel thro
ugh a
ugh a
potential barrier U
potential barrier U
0 0
even though the energy of the particle is
even though the energy of the particle is
less than U
less than U
0 0
.
.
2. 2.
With the increase in E, the transmission coefficient T increases
With the increase in E, the transmission coefficient T increases
.
.
3. 3.
If the width of potential barrier L increases then T decreases.
If the width of potential barrier L increases then T decreases.
This
This
tunneling phenomenon
tunneling phenomenon
provides the explanation for the
provides the explanation for the
alpha particle emission in certain radioactive
alpha particle emission in certain radioactive
nuclie
nuclie
. In this
. In this
case the alpha particle which has a few
case the alpha particle which has a few
MeV
MeV
energy can
energy can
escape from a nucleus whose potential wall is more than 25
escape from a nucleus whose potential wall is more than 25
MeV
MeV
. The probability of escape is however so small, i.e. the
. The probability of escape is however so small, i.e. the
alpha particle have to strike the wall 10
alpha particle have to strike the wall 10
38 38
or more times before
or more times before
it escapes.
it escapes.
Other applications: Field emission of electrons from cold metall Other applications: Field emission of electrons from cold metallic ic
surfaces, electrical breakdown of insulators, reverse breakdown surfaces, electrical breakdown of insulators, reverse breakdown of of
semiconductor diodes, switching action of tunnel diode. semiconductor diodes, switching action of tunnel diode.
28 28 PH 103 PH 103
The atomic structure
The atomic structure
Discovery of positive rays and electron at the end of nineteenth
Discovery of positive rays and electron at the end of nineteenth
century indicated that the atom consists of both positive and
century indicated that the atom consists of both positive and
negative charges. However the distribution of these charges was
negative charges. However the distribution of these charges was
not known. To understand this several theories regarding the
not known. To understand this several theories regarding the
structure of atom were proposed. The first one was the
structure of atom were proposed. The first one was the
Thomson
Thomson
s Plum Pudding Model

s Plum Pudding Model
.
.
Thomson model considered the atom as the homogeneous
Thomson model considered the atom as the homogeneous
sphere of positive charge with sufficient electrons
sphere of positive charge with sufficient electrons
embeded
embeded
in it
in it
so that the atom as a whole is electrically neutral. It is like
so that the atom as a whole is electrically neutral. It is like
pudding with plums distributed throughout.
pudding with plums distributed throughout.
This model failed to explain the observed frequencies of the
This model failed to explain the observed frequencies of the
optical spectra and also the alpha particle scattering experimen
optical spectra and also the alpha particle scattering experimen
t
t
done by
done by
Gieger
Gieger
and
and
Marsden
Marsden
.
.
29 29 PH 103 PH 103
The atomic spectra
The atomic spectra
Elements show its own characteristic emission spectrum,
Elements show its own characteristic emission spectrum,
consisting of discrete lines. The atomic spectra is, in general
consisting of discrete lines. The atomic spectra is, in general
,
,
very complicated but the Hydrogen spectrum is relatively simple.
very complicated but the Hydrogen spectrum is relatively simple.
This has tempted several scientists to develop an empirical
This has tempted several scientists to develop an empirical
formula for the wavelength of the lines observed.
formula for the wavelength of the lines observed.
Balmer
Balmer
(1885) proposed an expression for the wavelength of
(1885) proposed an expression for the wavelength of
hydrogen spectrum lines in the visible range.
hydrogen spectrum lines in the visible range.
Rydberg
Rydberg
(1890)
(1890)
used the same formula to describe the reciprocal of the
used the same formula to describe the reciprocal of the
wavelength.
wavelength.
,... 4 , 3 ;
1
2
1 1
2 2
=
= n
n
R
1
6 . 10967757

= m R
Rydberg
Rydberg
Constant
Constant
30 30 PH 103 PH 103
31 31 PH 103 PH 103
The Alpha particle scattering
The Alpha particle scattering
In this experiment
In this experiment
Gieger
Gieger
and
and
Marsden
Marsden
allowed fast moving alpha
allowed fast moving alpha
particles from
particles from
radan
radan
source to fall on a thin metallic foil and
source to fall on a thin metallic foil and
studied the angular distribution of the scattered alpha particle
studied the angular distribution of the scattered alpha particle
s. To
s. To
avoid the absorption of alpha particles the complete apparatus
avoid the absorption of alpha particles the complete apparatus
was placed in the vacuum.
was placed in the vacuum.
He observed that
He observed that
-
-
most of the alpha particles passed through the foil
most of the alpha particles passed through the foil
unaffected
unaffected
-
-
some of the alpha particles got scattered, a few were
some of the alpha particles got scattered, a few were
deflected at an angle greater than 90
deflected at an angle greater than 90
o o
and very few were
and very few were
backscattered
backscattered
collisions b/w alpha particles and electrons can not result in s
collisions b/w alpha particles and electrons can not result in s
uch
uch
a large angle scattering as the mass of alpha particle is almost
a large angle scattering as the mass of alpha particle is almost
7300 times larger than the mass of the electron.
7300 times larger than the mass of the electron.
Rutherford tried to explain these results by proposing
Rutherford tried to explain these results by proposing
Rutherford
Rutherford
s
s
Nuclear Model of atom
Nuclear Model of atom
32 32 PH 103 PH 103
Rutherford
Rutherford
s Nuclear Model
s Nuclear Model
Based on the results of alpha particle scattering experiment,
Based on the results of alpha particle scattering experiment,
Rutherford proposed that
Rutherford proposed that
-
-
atom consists of a tiny but massive positively charged region
atom consists of a tiny but massive positively charged region
called nucleus containing 99.9 % of the mass of the atom
called nucleus containing 99.9 % of the mass of the atom
surrounded by electrons at a distance
surrounded by electrons at a distance
-
-
the amount of positive charge = the amount of negative charge
the amount of positive charge = the amount of negative charge
-
-
electrons move in circular orbits around the nucleus. The
electrons move in circular orbits around the nucleus. The
electrostatic force between the positive and negative charges
electrostatic force between the positive and negative charges
provides the centripetal force necessary to maintain the orbital
provides the centripetal force necessary to maintain the orbital
motion. (If the electrons were at rest, they would be attracted
motion. (If the electrons were at rest, they would be attracted
towards the nucleus and collapsed )
towards the nucleus and collapsed )
33 33 PH 103 PH 103
Failures of Rutherford
Failures of Rutherford
s Nuclear Model
s Nuclear Model
According the Rutherford electrons move in circular orbits aroun
According the Rutherford electrons move in circular orbits aroun
d
d
the nucleus. Since the electrons are charged particle, if they
the nucleus. Since the electrons are charged particle, if they
move in circular orbits, they accelerate. And according to
move in circular orbits, they accelerate. And according to
classical electrostatics principles
classical electrostatics principles
-
-
accelerating charge radiates
accelerating charge radiates
energy hence electrons will also radiate energy. If so then the
energy hence electrons will also radiate energy. If so then the
energy of the electrons decreases and they will converge spirall
energy of the electrons decreases and they will converge spirall
y
y
into the nucleus. As a result the atom will not be stable.
into the nucleus. As a result the atom will not be stable.
If the electrons radiate energy continuously hence the emission
If the electrons radiate energy continuously hence the emission
spectrum should also be continuous however the experimental
spectrum should also be continuous however the experimental
results show the line spectrum.
results show the line spectrum.
34 34 PH 103 PH 103
Bohr Model of Hydrogen Atom
Bohr Model of Hydrogen Atom
Bohr retained the essential feature of the Rutherford
Bohr retained the essential feature of the Rutherford
s model but
s model but
extended his hypothesis by incorporating the Planck
extended his hypothesis by incorporating the Planck
s hypothesis.
s hypothesis.
-
-
electron revolves around the nucleus only in certain definite
electron revolves around the nucleus only in certain definite
circular orbits without radiating energy. These orbits are call
circular orbits without radiating energy. These orbits are call
ed
ed
stationary states
stationary states
-
-
The allowed states are those for which the orbital angular
The allowed states are those for which the orbital angular
momentum of electron is equal to integer multiple of
momentum of electron is equal to integer multiple of
where is the radius of n
where is the radius of n
th th
circular orbit.
circular orbit.
-
-
When electron jumps from higher energy state to the lower
When electron jumps from higher energy state to the lower
energy state, radiation is emitted.
energy state, radiation is emitted.
h
,... 3 , 2 , 1 , = = n n mvr
n
h
n
r
1 2
n n
E E h =
35 35 PH 103 PH 103
Radius of orbit and Energy of electron (Bohr Model)
Radius of orbit and Energy of electron (Bohr Model)
,... 3 , 2 , 1 , = = n n mvr
n
h
The attractive force between the electron and proton (in nucleus
The attractive force between the electron and proton (in nucleus
)
)
provides the centripetal force required for the circular motion:
provides the centripetal force required for the circular motion:
n n
r
mv
r
ke
2
2
2
=
2 2 9
0
10 9 . 8
4
1

= = C Nm k
2
2
mv
r
ke
n
=
By combining above two equations, we obtain
By combining above two equations, we obtain
0
2
2
2 2
a n
kme
n
r
n
= =
h
Here a
Here a
0 0
is the radius of first Bohr orbit and known as
is the radius of first Bohr orbit and known as
Bohr Radius
Bohr Radius
o
A meter
kme
a 53 . 0 10 53 . 0
10
2
2
0
= = =

h
0
a
36 36 PH 103 PH 103
The potential energy of the electron in n
The potential energy of the electron in n
th th
orbit :
orbit :
2
2
n
r
ke
U =
Total energy of the electron
Total energy of the electron
eV
n n
me
n
e mk
U T E
2 2 2 2
0
2
4
2 2
4 2
6 . 13
32 2
= = = + =
h h
0
a
Substitute the value of
Substitute the value of
n
r
2 2
4 2
h n
e mk
U =
The kinetic energy
The kinetic energy
T
T
of the electron
of the electron
2 2
4 2
2
2 2
1
h n
e mk
mv T = =
37 37 PH 103 PH 103
Application of Schr
Application of Schr
dinger equation to Hydrogen Atom

dinger equation to Hydrogen Atom
The very first real physical example, where natural
The very first real physical example, where natural
quantization occurs in wave mechanics, is Hydrogen Atom.
quantization occurs in wave mechanics, is Hydrogen Atom.
A hydrogen atom consists of a proton (a particle with electric
A hydrogen atom consists of a proton (a particle with electric
charge +e) and an electron (a particle of electric charge
charge +e) and an electron (a particle of electric charge
e).
e).
For convenience, we consider that the proton is stationary
For convenience, we consider that the proton is stationary
and electron is moving about in its vicinity but can not
and electron is moving about in its vicinity but can not
escape from the electric field of proton.
escape from the electric field of proton.
The potential energy for the hydrogen atom is
The potential energy for the hydrogen atom is
r
e
U

=
0
4
1

38 38 PH 103 PH 103
The Three dimensional Schr
The Three dimensional Schr
dinger equation
dinger equation
) , , ( ) , , (
2
2
2
2
2
2
2 2
z y x E z y x U
z y x m

= +
h
Since the potential energy is function of distance r, so either
Since the potential energy is function of distance r, so either
we have to represent r in terms of x, y and z or to represent
we have to represent r in terms of x, y and z or to represent
the Schr
the Schr
dinger equation in spherical polar co

dinger equation in spherical polar co
-
-
ordinates
ordinates

cos
sin sin
cos sin
r z
r y
r x
=
=
=
2 2 2 2
z y x r + + =
x
y
r
z
1
1
tan
cos
=
=

39 39 PH 103 PH 103
Schr
Schr
dinger equation in polar co

dinger equation in polar co
-
-
ordinates
ordinates
0
4
2
sin
1
sin
sin
1 1
0
2
2
2
2
2 2
2
2
=
+ +
r
e
E
m
r r r
r
r r
h
) ( ) ( ) ( ) , , ( = r R r
It is a partial differential equation, we use variable separatio
It is a partial differential equation, we use variable separatio
n
n
technique to solve it.
technique to solve it.
0
2
2
2
= +
l
m
d
d
Separate equation for all three functions

Separate equation for all three functions
40 40 PH 103 PH 103
0
sin
) 1 ( sin
sin
1
2
2
=
+ +

l
m
l l
d
d
d
d
0
) 1 (
4
2 1
2
0
2
2
2
2
=
+ +
R
r
l l
E
r
e m
dr
dR
r
dr
d
r h
l
im
Ae = ) (
) 2 ( ) ( + =
1
2
=
l
m i
e

... , 2 , 1 , 0 =
l
m
m
m
l l
is known as
is known as
magnetic quantum number
magnetic quantum number
.
.
Solutions:
Solutions:
(i)
(i)
Azimuthal
Azimuthal
wave equation:
wave equation:
41 41 PH 103 PH 103
2
1
= A
(ii) Polar wave equation:
(ii) Polar wave equation:
This equation has solution only when is an integer equal to
This equation has solution only when is an integer equal to
or greater than the absolute value of .
or greater than the absolute value of .
l
im
e
2
1
) ( =
l
l m
l
= ..., , 2 , 1 , 0
is known as
is known as
orbital quantum number
orbital quantum number
.
.
Normalization of
Normalization of
Azimuthal
Azimuthal
wave function will lead to the result
wave function will lead to the result
l
m
l
) (cos
)! ( 2
) )( 1 2 (
) (
l
m
l
l
l
P
m l
m l l
+
+
=
) 1 cos 3 (
2
1
) (cos
cos sin 3 ) (cos , cos ) (cos
sin ) (cos , 1 ) (cos
2 0
2
1
2
0
1
1
1
0
0
=
= =
= =

P
P P
P P
where is the associated
Legendre function
l
m
l
P
42 42 PH 103 PH 103
(iii) Radial wave equation:
(iii) Radial wave equation:
This equation has the energy term.
This equation has the energy term.
... , 3 , 2 , 1 = n
2 2 2
0
4
2 2 2
0
2
4
1
8
1
32 n h
me
n
me
E
n

= =
h
is known as
is known as
Principal quantum number.
Principal quantum number. n
must be a positive integer equal to or greater than
must be a positive integer equal to or greater than
n
) 1 ( + l
1
) 1 (

+
n l
l n
where is the associated Laguerre function.
0
, ,
a
r
l n
l
l n
e L r R
=
l n
L
,
43 43 PH 103 PH 103
) ( ) (
) (r R
l n
) ( ) ( ) ( ) , , ( = r R r
Complete Hydrogen wave functions:
Complete Hydrogen wave functions:
) ( 10 292 . 5
4
11
2
2
0
0
radius BOHR meter
me
a

= =
h
where
where
44 44 PH 103 PH 103
Significance of Quantum Numbers:
Significance of Quantum Numbers:
Principal quantum number
Principal quantum number
(Quantization of Energy)
(Quantization of Energy)
... , 3 , 2 , 1 = n
2 2 2
0
2
4
1
32 n
me
E
n
h
=
Orbital quantum number
Orbital quantum number
(Quantization of Angular momentum)
(Quantization of Angular momentum)
) 1 ( ..., , 3 , 2 , 1 , 0 = n l h ) 1 ( + = l l L
Magnetic quantum number
Magnetic quantum number
(Quantization of Angular
(Quantization of Angular
momentum direction)
momentum direction)
l m
l
= ..., , 2 , 1 , 0 h
l z
m L =
) 1 ( ) 1 (
cos
+
=
+
= =
l l
m
l l
m
L
L
l l z
h
h
Space quantization
Space quantization
45 45 PH 103 PH 103
46 46 PH 103 PH 103
47 47 PH 103 PH 103
48 48 PH 103 PH 103
Electron Spin
Electron Spin
Similar to the earth motion around the sun (orbital motion and
Similar to the earth motion around the sun (orbital motion and
spinning motion of the earth on its own axis), the electron
spinning motion of the earth on its own axis), the electron
also exhibits two kinds of motion around the nucleus:
also exhibits two kinds of motion around the nucleus:
1. 1.
Orbital motion
Orbital motion
2. 2.
Spinning motion
Spinning motion
The angular momentum due to the orbital motion is given by
The angular momentum due to the orbital motion is given by
(orbital angular momentum)
(orbital angular momentum)
Where
Where
l
l
is orbital quantum number.
is orbital quantum number.
The angular momentum due to the spinning motion is given by
The angular momentum due to the spinning motion is given by
(spin angular momentum)
(spin angular momentum)
h ) 1 ( + = l l L
h ) 1 ( + = s s S
Where
Where
s
s
is spin quantum number
is spin quantum number
2
1
= s
49 49 PH 103 PH 103
S L J + =
Hence an electron
Hence an electron
s motion can be specified completely if all the

s motion can be specified completely if all the
four quantum numbers are known.
four quantum numbers are known.
Total angular momentum of electron
Total angular momentum of electron
The possible value of z
The possible value of z
-
-
component of spin angular momentum
component of spin angular momentum
h
s z
m S =
2
1
2
1
= or m
s
These two possibilities are known spin up and spin down
These two possibilities are known spin up and spin down
50 50 PH 103 PH 103
Magnetic moment of electron:
Magnetic moment of electron:
Orbiting of an electron in circular orbit acts like a small curr
Orbiting of an electron in circular orbit acts like a small curr
ent loop.
ent loop.
We know from the classical electromagnetic theory that the curre
We know from the classical electromagnetic theory that the curre
nt
nt
loop produces magnetic field as well as responds to the external
loop produces magnetic field as well as responds to the external
field.
field.
If A is the area of the loop carrying current
If A is the area of the loop carrying current
I,
I,
which is placed in the
which is placed in the
magnetic field B then it experience a torque
magnetic field B then it experience a torque
The vector is the magnetic moment. The torque tends
The vector is the magnetic moment. The torque tends
to turn
to turn
the loop in such a way that points in the same direction a
the loop in such a way that points in the same direction a
s B.
s B.
Potential energy
Potential energy
sin B B B iA = = =
r
r

= = = =
0
2
0
2
cos sin

B B d B d U
m
r
r
51 51 PH 103 PH 103
Consider a current loop of radius r and period T.
Consider a current loop of radius r and period T.
The total current is charge passing at any point of the orbit in
The total current is charge passing at any point of the orbit in
unit
unit
time
time
v
v
is the speed of electron.
is the speed of electron.
Magnetic moment of electron is:
Magnetic moment of electron is:
Since angular momentum of electron then
Since angular momentum of electron then
The negative sign is due to the fact that L and are in opp
The negative sign is due to the fact that L and are in opp
osite
osite
direction.
direction.
r
v
e
T
e
i
2
= =
vr m L
e
=
evr r
r
ev
iA
2
1
2
2
= = =
L
m
e
e
r
r
2
=

52 52 PH 103 PH 103
If we consider an atom in which the spin angular moment due to s
If we consider an atom in which the spin angular moment due to s
pin
pin
cancel out e.g. He
cancel out e.g. He
In absence of magnetic field the atom has energy E
In absence of magnetic field the atom has energy E
0 0
Since the magnetic moment of electron depends on the angular
Since the magnetic moment of electron depends on the angular
momentum vector. We know that the orbital angular momentum has
momentum vector. We know that the orbital angular momentum has
(2l+1)
(2l+1)
possible orientations. Hence the electron magnetic moment
possible orientations. Hence the electron magnetic moment
will also has
will also has
(2l+1)
(2l+1)
orientations.
orientations.
As we have seen that in presence of magnetic field there is chan
As we have seen that in presence of magnetic field there is chan
ge
ge
in energy by i.e.,
in energy by i.e.,
B
r
r

B L
m
e
B E
e
r r r
r
= =
2
If we consider that the magnetic field is applied in z

If we consider that the magnetic field is applied in z
-
-
direction then
direction then
B m B m
m
e
B L
m
e
E
l B l
e
z
e
= = =
2 2
h
r
Zeeman
Zeeman
Effect: Splitting of energy levels in presence of magnetic fiel
Effect: Splitting of energy levels in presence of magnetic fiel
d
d
53 53 PH 103 PH 103
2 24
10 27 . 9
2
Am
m
e
e
B
= =
h
Bohr
Bohr
Magneton
Magneton

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Dr. Dr.

Vinod Vinod Patidar Patidar

law if the force acting on the particle (or

s (first order differential equations)

s law it is also written for a certain value of

dinger equation is to obtain the

Dr. Dr. Vinod Vinod Patidar Patidar

dinger equation with U=0

dinger equation separately for the

dinger equation, the equation

Dr. Dr. Vinod Vinod Patidar Patidar

> < > <

On applying the condition that the wave function must be finite

Dr. Dr. Vinod Vinod Patidar Patidar

dinger equation for region (1)

dinger equation for region (3)

dinger equation for region (2) (if we also assume E<

Since there is no particle coming from right to left in the regi

s Plum Pudding Model

dinger equation to Hydrogen Atom

Dr. Dr. Vinod Vinod Patidar Patidar

dinger equation in spherical polar co

Dr. Dr. Vinod Vinod Patidar Patidar

dinger equation in polar co

Separate equation for all three functions

s motion can be specified completely if all the

Dr. Dr. Vinod Vinod Patidar Patidar

If we consider that the magnetic field is applied in z

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