De Broglie hypothesis:

Some phenomena of electromagnetic radiation like interference, diffraction and polarization

shall be explained only based on wave theory. Similarly, other phenomena like blackbody radiation,
Compton Effect and photoelectric effect exhibited by electromagnetic radiation shall be explained only
based on particle theory.

Hence, it can be concluded that radiation behaves as wave in certain environment and in other
environment, it also behaves as particle. However, wave and particle properties are not exhibited
simultaneously. This is called dual nature of radiation.

As logical extension to dual nature, it can be said that the matter which we observe as particle
also exhibit wave nature under certain conditions. This is the basis for de Broglie hypothesis.

In 1924, de Broglie proposed that just like radiation, matter also possesses wave nature in
addition with particle properties. But both wave and particle are not exhibited simultaneously. The
wavelength for such matter wave is calculated as follows.

de Broglie wavelength:

Consider a photon of mass ‘m’ moving with velocity ‘c’, the energy of photon is given by Einstein mass
energy relation as follows
2
E=m c −−−−−(1)

According to Plank’s theory of radiation, the energy of photon with frequency 𝛾 is given by

E=h−−−−−−(2)

Equating equations 1 and 2

2
m c =h

but  = 𝑐/ , hence

2 c
m c =h
❑
Or

h
¿
mc

but momentum p=m × c

Therefore λ = ℎ/ , this is known as de Broglie wavelength.

Characteristics of matter waves

the particle is 𝜆 = ℎ/𝑚𝑣 or 𝜆 = ℎ/𝑝 .

(i) A particle of mass ‘m’ moving with velocity ‘v’ , then the wavelength of wave associated with

(ii) Matter wave is different from electromagnetic waves

(iii) The matter wave associated with a particle is independent to the charge of that particle.
(iv) The velocity of matter wave is not constant like electromagnetic radiation, but it depends on
the velocity of particle associated with it.
(v) The velocity of matter wave is normally greater than the velocity of light.
(vi) If the mass of particle is small, the wavelength associated with that particle is greater and
visa vice
(vii) If velocity of particle is zero then wavelength will be indeterminate. If v=∞ , then λ=0. This
means that the matter waves are generated by motion of the particle.

De Broglie wavelength in terms of KE: Consider a particle of mass m moving with a

velocity v. Then, the kinetic energy (KE) of the particle is

1 2
E= m v
2
2
1 2 2 p
¿ m v=
2m 2m

Hence the momentum is

p= √ 2 mE

The associated wavelength is

h
¿
√2 mE
The above equation represents the de Broglie wavelength in terms of kinetic energy.

De Broglie wavelength of Electron volt: Consider an electron of mass m and charge e that is
accelerated through a potential difference of V volts. Then, the KE of the electron is equal to the
loss in potential energy and is given by

1 2
m v =eV
2
2 2
m v =2 m eV

p=mv= √ 2 meV

Then de Broglie wavelength of electron is

 h
¿
√2 meV
Substituting the value of h (=6.626 x 10-34), e (=1.6 x 10-19) and m (=9.1 x 10-31)

We get,

12.28× 10−10
¿ m
√V
12.28 o
¿ A
√V
The above equation gives the de Broglie wavelength of an electron.

Phase Velocity:

For a wave with no damping, the equation for displacement is given by,

y= A sin (ωt−kx)

Where, y is the displacement along Y coordinate at the instant t, , the angular frequency, k is
the propagation constant or wave number and x is the displacement along X-coordinate at the
instant t. The term (t-kx) gives the phase of the oscillation. This term will be same for all
uniphase points in a periodic wave. That implies

d
( ωt−kx )=0
dt

ω−k ( dxdt )=0

dx ω
=
dt k

The velocity with which such point would propagate is called phase velocity. Here x is the
distance travelled. Hence (dx/dt) is taken as phase velocity. Hence

ω
v p h ase=
k

Group Velocity

When a group of two or more waves, differing slightly in wavelengths are superimposed
on each other, a resultant pattern emerges in the shape of variation in amplitude. Such variation
represents the wave group as a whole and is called wave packet. Since the group consists of
waves of different wavelengths they are bound to move with different velocities in a dispersive
medium, at which time the envelope or the wave packet is carried with a velocity which will be
different from others. The velocity with which the wave packet moves is called group velocity.

Expression for group velocity:

Let us consider two waves of same amplitude with slightly different frequency and wave
vector moves through the space. The resultant wave is summation of these two waves.

y 1= A sin ( ωt −kx ) (1)

y 2= A sin ((ω+∆ ω )t−(k + ∆ k )x)(2)

y= y 1+ y 2 =A sin(ωt−kx)+ A sin ((ω+∆ ω)t−(k + ∆ k )x )

a−b a+b
sin a+ sin b=2 cos sin
2 2

Hence,

y=2 A cos ( ∆ 2ω t − ∆ 2k x ) sin ( ( 2 ω+∆2 ω ) t − ( 2 k +∆2 k ) . x )(3)

Since >>  and k>>k, the above equation can be written as,

y=2 A cos ( ∆ 2ω t − ∆ 2k x ) sin ( ωt−kx ) ( 4)

Comparing eqn (1) and eqn (4), the coefficient of sin(t – kx) is amplitude in the both equation.
In eqn(1) the amplitude is constant and in eqn (4) the amplitude is given by the eqn,

2 A cos ( ∆ 2ω t − ∆ 2k x )
Is not constant with varies with wave. The velocity with which the amplitude transmitted in the
resultant wave is group velocity and is given by,

v group =
( 2 ) ∆ω
∆ω
=
( 2 ) ∆k
∆k

In the limit,

∆ ω dω
❑
∆ k → dk
 dω
v group =
dk

Relation between group velocity and phase velocity:

We have phase velocity and group velocity as

dω
v group =
dk

ω
v p h ase=
k

Where  is the angular frequency of the wave and k be the wave vector,

ω=k . v ph

dω d v ph
v group = =v ph+ k .
dk dk

d v ph d
v group =v ph+ k .
d dk

But,

2π
k=
❑
dk −2 π
= 2
d ❑

( )
d v ph 2 π −❑2
v group =v ph+ .
d ❑ 2π

d v ph
v group =v ph−
d

The above eqn represents the relationship between phase velocity and group velocity.

Relationship between Particle velocity and group velocity”:

We have the equation for group velocity as

dω
v group = (1)
dk

But,
 E
ω=2 π =2 π (2)
h

dω= ( 2hπ ) dE( 3)

Also we have,

2π p
k= =2 (4)
❑ h

dk = ( 2hπ ) dp(5)
Dividing eqn(3) by eqn(5), we have

dω dE
= (6)
dk dp

Also, we know that,

2
p
E=
2m

dE 2 p p
= =
dp 2 m m

Using the above eqn in eqn(6),

dω p
=
dk m

But, p= mvparticle, where vparticle is the particle velocity, then

dω m v particle
= =v particle (7)
dk m

Hence,

v group =v particle

Therefore, the de Broglie group associated with the particle travelling with the velocity equal to
the velocity of particle itself.

Heisenberg’s Uncertainty Principle:

 It is impossible to determine simultaneously both the position and momentum of a
particle accurately. Any effort made to make a measurement very accurately of the position of
the particle such as a electron results in a large uncertainty in the measurement of momentum
and vice versa. The measured values cannot have accuracies exceeding what is permitted under
the condition,

h
∆ x . ∆ px ≥
2π

Where x and px be the uncertainties in the measurements of position and momentum of
particle. The uncertainty principle could also be expressed in terms of the uncertainties involved
in the measurement of energy and time

h
∆ E . ∆ t ≥( )
4π

The pair x and px is said to be conjugate and so is the pair E and t.

Non-existence of electron in the nucleus (Non-relativistic case):

Heisenberg’s uncertainty principle states that,

h
∆ x . ∆ px ≥
2π

Which can also be written as

h
∆ px ≥
4π∆x

The typical value of diameter of nucleus is of the order of 10 -14m. We can take this value to be
approximately the maximum space of confinement. This is the uncertainty in position of electron
in the nucleus. Then,
−34
6.63× 10
∆ px ≥ −14
4 π ×10

Or,
−20
∆ p x ≥ 0.5 ×10 Ns

Which is the uncertainty in the momentum of the electron. But since the momentum of the
electron must at least be equal to the uncertainty in the momentum, we can state that,

−20
p x ≥ 0.5 ×10 Ns
The energy of the body can be written as
2
p
E=
2m

Since the mass of the electron is 9.11X10-31 kg, we can say that, in order that the electron may
exist within the nucleus, its energy E must be such that,
2
( 0.5 × 10−20 )
E≥ −31
2 × 9.11× 10
−11
E ≥ 1.372× 10 J

Expressing in eV, we get,

−11 18
E ≥ 1.372× 10 ×6.24 ×10 eV

Or

E ≥ 85 MeV

This means that in order to exist in nucleus the energy of the electron must be greater than or
equal to 85 MeV. But, the experimental investigations on beta-decay emission reveal that, the
kinetic energy of the beta particles of the order ot 3 to 4 MeV. This cleary indicates that, the
emitted electrons cannot be the ones which existed within the nucleus prior to -emission.
During -emission, a proton decays into a neutron and an electron. This electron is ejected
instantaneously out of the nucleus at the moment it is formulated.

Time independent Schrodinger equation

The wave function of a particle describing de Broglie wave is given by following

equation,
i(ωt−kx )
¿ Ae

Where  be the total wave function, A, be the amplitude of the wave,  be the angular
frequency, t be the time, k be the wave vector.

The space independent part in eqn (1) can be represented as

ikx
φ= A e

Hence the eqn (1) becomes,

 −iωt
¿φe

Let us differentiate  twice with respect to x. Since  depends on x,

2 2
d −iωt d φ
2
=e 2
dx dx

Now, again differentiating  twice, with respect to time t, we have,

2
d 2 −iωt
2
=−ω e φ
dt

We have the equation for a travelling wave as,

2 2
d y 1 d y
2
= 2 2
dx v dt

Where y is the displacement and v is the velocity of the wave. By analogy, we can write the
wave equation for de Broglie wave for the motion of a free particle as,
2 2
d 1 d
2
= 2 2
d x v dt

Substituting the values above we get,

2
d φ 1(
= 2 −ω e φ )
−iωt 2 −iωt
e 2
dx v
2 2
d −ω
2
= 2
dx v

If  and  be the wave length and frequency of the wave, then =2 and v=. Substituting for
 and v, the above eqn becomes,
2 2
d −4 π
2
= 2
dx ❑
2
1 1 d
2
= 2 2
❑ 4π dx
2 2
p h 1
Kinetic energy= =
2m 2m ❑2

Substituting for 1/2 we get,

 2 2
−h 1 d
Kinetic energy=
8π m ❑ d x
2 2

Let there be a field where the particle is present. Depending on its position in the field, the
particle will posses certain potential energy V. Then the total energy is sum of the potential and
kinetic energy. Hence,
2 2
−h 1 d
E= +V
8π m ❑ dx
2 2

2 2
−h 1 d
=E−V
8π m ❑ d x
2 2

2 2
d −8 π m (
2
= 2
E−V )
dx h
2 2
d 8π m
2
+ 2 ( E−V )=0
dx h

The is the time-independent Schrodinger’s equation in one-dimension. For three dimension

above equation becomes

2 2 2 2
d d d 8π m
2
+ 2 + 2 + 2 ( E−V )=0
dx d y d z h

Probability density (Born’s interpretation)

If we consider a single particle and  is the wave function associated with the particle,
then ||2 is the probability per unit volume that the particle will be found at the given region. Let
 be a volume inside which a particle is known to be present, but where exactly the particle
situated inside  is not known. Then the probability of finding the particle in a certain element of
volume d of  is given equal to ||2 d. For this reason the ||2 is called the probability density
or probability function as per Born’s interpretation.
The probability of occurrence is a real and positive quantity. But wave functions may be
complex. Hence in order to get a value that is positive and real while evaluating ||2, the wave
function  is multiplied with its complex conjugate *. The product * is always a positive
and real quantity and corresponds to meaningful definition of probability.

Normalization:

If  is the wave function associated with a particle then we have ||2 d as the probability
of finding the particle in the volume d. Further, if we are certain to the extent that the partile is
definitely present in a particular region or space of volume , then as per the statistical rule,
❑

∫ ¿∨¿2 d=1 ¿
0

The value 1 for probability means, it is clearly a certainty. If we are not all certain about locating
the particle in a finit volume anywhere in space, then the expectation will bcome limited to the
extent that it exist somewhere in space, then the probability becomes,
∞

∫ ¿∨¿2 d=1 ¿
−∞

But in most cases, the result of valuation of above equation will not be unity, but involves a
constant that existed in the equation for . However, the actual result whatever obtained is
equated to unity and the value of the constant is determined and is substituted in the equation for
. This process is called normalization.

Properties of the Wave function:

1. The , wave function is single valued everywhere.

2.  is finite everywhere
3.  and its first derivatives with respect to its variable are continuous everywhere
4. For bound states,  must vanish at infinity. If  is a complex function, then * must
vanish at infinity.

Eigen function and Eigen values:

 The wave functions which possess the three essential properties – finite, single valued,
continuity of both wave function and its first derivatives in the region of space – are known as
eigen functions. The wave functions which satisfy the above three properties are solved only for
certain values of energies under steady state conditions known as eigen value and corresponding
wave function  known as eigen function. One can extract information from a wave function by
means of a mathematical operation called an operator. The operator operates on the wave
function and reproduces the eigen function and its energy. The most important operators are of
energy (H- Hamiltonian), position and momentum.

For example, the total energy operator, H operates on the wave function and reproduces
its corresponding wave function  and energy as

H=E

The energy values obtained during the above operation are known as eighen values. Similarly,
when the momentum eigen values are obtained when a momentum operator operates on the wave
function .

Physical observable operator Operator symbol

Momentum h ∂ P
2 πi ∂ x

Kinetic energy h
2
∂
2
T
2 2
8π m ∂ x

Total Energy 2 2 H
h ∂
2 2
+U
8π m ∂ x

Position x
x

Applications of Schrodinger wave equation – particle in a box

 Consider a one-dimensional box with width x=0 to x=L and infinite height as shown in
Fig. Inside the box potential energy is zero (V=0) and outside its value is infinite. The particle
moves freely with energy E inside the box. Since V= outside the box the wave function is zero
in this region (0xL)., =0 and ||=0. But in the region 0<x<L the wavefunction ||0.
According to Schrodinger, the one-dimensional time independent wave equation is
2
d 2m
2
+ 2 ( E−V )=0
dx h

For free particle V=0, Hence

2
d 2m
2
+ 2 E=0
dx h

2
d 2
2
+ k =0
dx

Where

2m 2
2
E=k
h

The solution of the above equation gives the wave function of the particle inside the bos,

¿ A sin kx + B cos kx

Where A is the amplitude of the wave function. Applying the boundary conditions, when x=0
and =0, we get B=0.

Similarly when x=L and =0 and we get,

 0=A sin kL

Since the particle present inside the box, and hence A0. And hende sin(kL)=0. It is only
possible when kL=n. Hence,

nπ
k=
L

Hence the solution of the wave function becomes,

nπx
❑n= A sin
L

Normalization: One can determine the value of A by considering the definite existence of
particle inside the box. i.e.,
∞

∫ ¿ ¿ 2 dx=1
−∞

∫ A 2 si n2 ( nπx
L )
dx=1
0

L
1
A
2 ∫
= si n
0
2 n πx
L
dx ( )

[ ]
2 πnx
L 1−cos ⁡( )
1 L
2 ∫
= dx
A 0 2

Integrating above equation and putting the limit we get,

1 L
=
A 2
2

A=
√ 2
L

Hence the wave function becomes,

❑n=
√ 2
L
sin
nπx
L

The energy eigen value corresponding to the above wave function is,
 2 2 2 2 2 2 2
h k n π h n h
En = = 2 2
= 2
2m L 8 π m 8m L

The above equation gives energy eigen values E n of a particle in an infinite potential well for
each value of n=1,2,3, etc.

Energy eigen value, probability density, wave function of particle in a box

Case 1: When n=1, it is known as ground state. The particle is definitely present inside the
ground state in the well. The wave function and the corresponding energy is obtained by
substituting n=1 as,

wavefunction ❑1=
√ 2
L
sin
πx
L
2
h
Energy eigenvalue E1= 2
8mL

2 2 2 πx
Probability density|| = sin
L L

Where E1 is known as ground state energy. The plot of wave function and the probability
density in the box is given in the Fig.

At the boundary condition, i.e., x=0 and x=L, the wave function =0. It indicates that the
probability of finding the particle is also zero at the boundary ||=0 and the it has the maximum
probability at the center x=L/2.
Case II: When n=2, the particle enter into the excited state known as first excited state.
Therefore, the wave function and the corresponding energy of the particle in first excited state is
obtained as

❑2=
√ 2
L
sin
2 πx
L
2
2 h
E2=2 2
8mL

2 2 2 2 πx
Probability density |❑2| = sin
L L

The normalized wave function and the probability density function corresponding to n=2 is given
in Fig. The particles absent at x=0, x=L/2 and x=L. The maximum probability exists at x=L/4
and 3L/4.

Case III: When n=2, the particle enter into the excited state known as first excited state.
Therefore, the wave function and the corresponding energy of the particle in first excited state is
obtained as

❑2=
√ 2
L
sin
3 πx
L
2 2
2 h 9h
E2=3 2
= 2
=9 Eo
8mL 8mL

2 2 2 3 πx
Probability density |❑2| = sin
L L
The normalized wave function and the probability density function corresponding to n=2 is given
in Fig. The particles absent at x=0, x=L/3, 2L/3, and x=L. The maximum probability exists at
x=L/6, L/2, and 5L/ as shown in the fig.