Wave Mechanics

Wave function
Wave function, ψ is a quantity associated with a moving particle. It
is a complex quantity.

|Ψ|2 is proportional to the probability of finding a particle at a

particular point at a particular time. It is the probability density.

|  |2   *
ψ is the probability amplitude.

Thus if   A  iB then  *  A  iB

2 2 2 2 2 2
|  |   *  A  i B  A  B
 Normalization

|Ψ|2 is the probability density.

The probability of finding the particle within an element of volume dV
2
|  | dV
Since the particle is definitely be somewhere, so

2
 |  | dV  1


A wave function always follows the normalization equation.

 Properties of wave function
1. It must be finite everywhere.
If ψ is infinite for a particular point, it mean an infinite large
probability of finding the particles at that point. This would
violates the uncertainty principle.
2. It must be single valued.
If ψ has more than one value at any point, it mean more than one
value of probability of finding the particle at that point which is
obviously ridiculous.

3. It must be continuous and have a continuous first derivative

everywhere.
  
, , must be continuous
x y z
4. It must be normalizable.
 Linearity and Superposition
If ψ1 and ψ2 are two solutions of any Schrodinger equation of a
system, then linear combination of ψ1 and ψ2 will also be a solution
of the equation..
  a1 1  a2 2 is also a solution
Here a1 & a2are constants
Above equation suggests:
(i) The linear property of Schrodinger equation
(ii) ψ1 and ψ2 follow the superposition principle

If P1 is the probability density corresponding to ψ1 and P2 is the

probability density corresponding to ψ2

Then    1  2 due to superposition principle

Total probability will be P |  |2 |  1  2 |2
 ( 1  2 )* ( 1  2 )  ( 1*  2* )( 1  2 )
  1* 1  2* 2  1* 2  2* 1
P  P1  P2  1* 2  2* 1 P  P1  P2
Probability density can’t be added linearly
Expectation values
Expectation value of any quantity f(x) (which is a function of ‘x’ ), is
given by 
2
 f (x)  

 f ( x) | | dx
Thus expectation value for position ‘x’ is

2
x   x |  | dx

Expectation value is the value of ‘x’ we would obtain if we
measured the positions of a large number of particles described by
the same function at some instant ‘t’ and then averaged the results.

Q. Find the expectation value of position of a particle having wave

function ψ = ax between x = 0 & 1, ψ = 0 elsewhere.

Solution 1 1
 x    x |  |2 dx  a 2  x 3dx
0 0

4 1
x 
2
a  
 4 0
a2
x 
4
 Operators
An operator is a rule by means of which, from a given function
we can find another function.
i
For a free particle 
( Et  px )
  Ae
 i
^  
Then  p Here p (i)
x  i x
is called the momentum operator

Similarly  i ^ 
  E Here E  i (ii)
t  t
is called the Total Energy operator

Equation (i) and (ii) are general results and their validity is the
same as that of the Schrodinger equation.
 Schrodinger’s time dependent wave equation
Wave equation for a free particle moving in +x direction is
i
( Et  px )
  Ae  (i)

where E is the total energy and p is the momentum of the particle

Differentiating (i) twice w.r.t. x
 2 p2 2 2  2

2
 2  p    2
(ii)
x  x
Differentiating (i) w.r.t. t
 iE 
   E  i (iii)
t  t
 For non-relativistic case
E = K.E. + Potential Energy

p2
E  Vx , t
2m
p2
 E    V (iv)
2m
Using (ii) and (iii) in (iv)

  2  2
i  2
 V
t 2m x

This is the time dependent Schrodinger’s wave equation for a

particle in one dimension.
 Schrodinger’s time independent wave equation
One dimensional wave equation for the waves associated with a
moving particle is
2x
  A sin (i)

where
ψ is the wave amplitude for a given x.
A is the maximum amplitude.
λ is the wavelength
From (i)
 2 4 2 2x
2
  2 A sin
x  
 2 4 2
2
 2  (ii)
x 
 h 2 2 1 2
 1 mo v 2mo  mo v  1 2mo K
 2   2  so, 
mo v  h 2
 2
h2
h2
where K is the K.E. for the non-relativistic case
Suppose E is the total energy of the particle
and V is the potential energy of the particle

1 2mo
2
 2 (E  V ) (iii)
 h
Equation (ii) now becomes

 2 4 2
2
  2 2mo ( E  V )
x h
 2 2mo
2
 2 ( E  V )  0
x 
This is the time independent (steady state) Schrodinger’s wave
equation for a particle of mass mo, total energy E, potential energy
V, moving along the x-axis.
If the particle is moving in 3-dimensional space then

 2  2  2 2mo
2
 2  2  2 ( E  V )  0
x y z 
2 2mo
   2 ( E  V )  0

This is the time independent (steady state) Schrodinger’s wave
equation for a particle in 3-dimensional space.

For a free particle V = 0, so the Schrodinger equation for a free

particle
2 2mo
   2 E  0

 Heisenberg Uncertainty Principle
It states that only one of the “position” or “momentum” can be
measured accurately at a single moment within the instrumental limit.
x  uncertainty in position
p x  uncertainty in momentum
 h
then x.p x   
2 2

The product of x & p x of an object is greater than or equal to
2
If x is measured accurately i.e. x  0  p x  
The principle applies to all canonically conjugate pairs of quantities
in which measurement of one quantity affects the capacity to measure
the other.

Like, energy E and time t. Et 
2 
and angular momentum L and angular position θ L 
2
 Applications of Heisenberg Uncertainty Principle
Determination of the position of a particle by a microscope
Suppose we want to determine accurately the position and momentum
of an electron along x-axis using an ideal microscope free from all
mechanical and optical defects.
The limit of resolution of the
microscope is
2d sin   n 

x 
2 sin i
Scattered
here i is semi-vertex angle of the cone i Photon
of rays entering the objective lens of
the microscope. Incident
x is the order of uncertainty in the Photon Recoiled electron
x-component of the position of the
electron.
We can’t measure the momentum of the electron prior to illumination.
So there is uncertainty in the measurement of momentum of the
electron.
The scattered photon can enter the microscope anywhere between the
angular range +i to –i.
h
The momentum of the scattered photon is (de-Broglie) p

Its x-component can be given as 2h
p x  sin i

The x-component of the momentum of the recoiling electron has the
same uncertainty, p x (conservation of momentum)
The product of the uncertainties in the x-components of position and
momentum for the electron is
 2h 
x.p x   sin i x.p x  h 
2 sin i  2
This is in agreement with the uncertainty relation.
 Non-existence of electron in nucleus
Order of radius of an atom ~ 5 x10-15 m
If electron exist in the nucleus then (x) max  5 1015 m
 
xp x  (x) max (p x ) min 
2 2

(p x ) min   1.110  20 kg.m.s 1
2x
p2
then E  237.5MeV
2m
Thus the kinetic energy of an electron must be greater than 237.5
MeV to be a part of nucleus

Experiments show that the electrons emitted by certain unstable

nuclei don’t have energy greater than 3-4 MeV.

Thus we can conclude that the electrons cannot be present

within nuclei.
Energy of a particle in a box or infinite potential well
Let us consider a particle of mass m in infinite potential well
of width L. The maximum uncertainty in the position of
the particle may be
(x) max  L
From Uncertainty principle 
xp x 
2
Here, we can write, minimum uncertainty in momentum-
 
px  
 x max L
Since, the Kinetic Energy can be written as
p2
KE 
So, for present case 2m

 KE min 
2mL2
This is the minimum kinetic energy of the particle in an
infinite potential well
 Particle in a Box: Eigenvalue
Consider a particle of rest mass mo enclosed in a one-dimensional
box (infinite potential well).
V  V 
Boundary conditions for Potential V
0 for 0 < x < L
V(x)= {  for 0 ≥ x ≥ L particle

Boundary conditions for wave function ψ V 0

0 for x = 0
Ψ= {0 for x = L
x=0 x=L

Thus for a particle inside the box Schrodinger equation is

 2 2mo
2
 2 E  0 (i) [ V  0 inside ]
x 
 h 2
  (k is the propagation constant)
p k
p 2mo E
k  
 
2 2mo E
k  (ii)
2
Equation (i) becomes
 2 2
2
 k  0 (iii)
x
General solution of equation (iii) is

 ( x)  A sin kx  B cos kx (iv)

Boundary condition says ψ = 0 when x = 0

 (0)  A sin k .0  B cos k .0

0  0  B.1 B0
Equation (iv) reduces to
 ( x)  A sin kx (v)
Boundary condition says ψ = 0 when x = L

 ( L)  A sin k .L
0  A sin k .L
A  0  sin k .L  0
 sin k .L  sin n
 kL  n
n
k (vi)
L
Put this in Equation (v)
nx
 ( x)  A sin
L
(Where n = 1, 2, 3…., BUT n # 0 as this gives ψ = 0 everywhere)
Put value of k from (vi) in (ii)

2 2mo E
k 
2
2
 n  2mo E
   2
 L  
  k 2 2
n2h2
E  2
(vii)
2mo 8mo L
Where n = 1, 2, 3….
Equation (vii) concludes
1. Energy of the particle inside the box can’t be equal to zero.
The minimum energy of the particle is obtained for n = 1
h2
E1  (Zero Point Energy)
8mo L2
If E1  0 momentum  0 i.e. p  0
 x  
But xmax  L since the particle is confined in the box of
dimension L.
 Thus zero value of zero point energy violates the Heisenberg’s
uncertainty principle and hence zero value is not acceptable.

2. All the energy values are not possible for a particle in

potential well.
Energy is Quantized
3. En are the eigen values and ‘n’ is the quantum number.
4. Energy levels (En) are not equally spaced.
n=3

n=2 E3
n=1 E2
zero point energy
E1
 Particle in a Box: Eigenfunction
nx
 n ( x)  A sin
L
Using Normalization condition

2
|
 n ( x ) | dx  1

L
2 nx 2
A  sin dx  1
0
L
L
2 2
A   1  A 
2 L
The normalized eigen function of the particle are
2 nx
 n ( x)  sin
L L
 Probability density figure suggest that:
1. There are some positions (nodes) in the box that will never be
occupied by the particle.
2. For different energy levels the points of maximum probability are
found at different positions in the box.
|ψ1|2 is maximum at L/2 (middle of the box)
|ψ2|2 is zero L/2.
 Particle in a Three Dimensional Box

Eigen energy E  Ex  E y  Ez
2
h
E  (nx2  n y2  nz2 )
8mL2
Eigen function    x y z

nxx n yy nzz

  Ax Ay Az sin sin sin
L L L
3
 2 nxx n yy nzz

   sin sin sin
L  L L L
 