____________________________________________________________________________________________________

Material science

Paper No. : Quantum Mechanics

Module : Time dependent Schrodinger equation, Conservation of
Probability and Continuity equation

Development Team
Prof. Vinay Gupta, Department of Physics and Astrophysics,
Principal Investigator University of Delhi, Delhi

Prof. V. S. Bhasin (Retired) ,Department of Physics, University

Paper Coordinator
of Jammu, Delhi-110007

Content Writer Prof.V. S. Bhasin, (Retired),Department of Physics,

University ofDelhi, Delhi-110007

Content Reviewer

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Subject Physics

Paper No and Title Quantum Mechanics

Module No and Title 6 The time dependent Schrodinger equation, Conservation

of probability and Continuity equation
Module Tag V S Bhasin

TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Time-dependent Schrodinger equation, Conservation of Probability and

Continuity equation

3.1 The time- dependent Schrodinger equation

3.2 Generalization to three dimensions

4. Conservation of Probability and Continuity Equation

4.1 Probability conservation and the Hermiticity of the Hamiltonian

5. Admissability conditions required for the Schrodinger wave function

6. Summary

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1. Learning Outcomes

After studying this module, you shall be able to

 Learn how to develop the time dependent Schrodinger equation for a free particle
also for a particle moving in a field of force
 Know the three dimensional generalization of Schrodinger equation
 Learn to express the Schrodinger equation in operator form
 Learn how the normalization condition on the wave function leads to conservation
of probability and continuity equation.
 Know the admissibility conditions required for the Schrodinger wave function

2. Introduction

In the earlier module, we introduced the concept of wave function to describe the
properties of a physical system. We learnt that in the position representation, the wave

function  of a particle is a function of its space coordinates r and of time t. In this
module, we are concerned with the non-relativistic motion of a free particle as well as
that of a particle in a force field that can be represented by a potential energy. A
quantitative description of the motion in terms of a differential equation, the Schrodinger
equation is developed. In developing this equation we are guided by the principle (i) that
it should be linear and homogeneous equation so that superposition principle holds;( ii)
the results obtained by using the equation should agree with those of classical mechanics
in macroscopic situations in accordance with the correspondence principle and (iii) the
equation should be of first order in the time derivative so that the evolution of the system
is entirely determined once the wave function is known at a particular time. Using the
definition of position probability density and the condition that the probability of finding
the particle somewhere at time t is unity, we deduce the equation for conservation of
probability leading to the equation of continuity.

3. Time-dependent Schrodinger equation, Conservation of Probability and

Continuity equation

3.1 The time- dependent Schrodinger equation

Let us consider the non-relativistic one-dimensional motion of a free particle of

  
mass m with a well defined momentum p  p x x ( where x is a unit vector along the x-
axis) and energy E. We have seen in an earlier module that this particle is described by a
plane wave of wave number k= p x /  and angularfrequency   E /  , viz.,

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 ( x, t )  A exp(ikx  it )
(6.1)
 A exp[i( p x x  Et ) / ]

where A is a normalization constant. The angular frequency  is also related to the

wave number k by the relation   k 2 /(2m) , which corresponds to the classical relation

p x2
E (6.2)
2m

between the energy and momentum of the particle. Now, on differentiating Eq.(6.1) with
respect to time, we get

 E
 i  (6.3)
t 

and differentiating twice with respect to x, we have

 2 p x2
   (6.4)
x 2 2

Using Eq.(6.2), we find that plane wave (6.1) satisfies the partial differential equation

 2  2
i ( x, t )   ( x, t ) (6.5)
t 2m x 2

This is a linear and homogeneous equation which can also be satisfied by a linear
superposition of plane waves (6.1). Thus, the plane wave packet


( x, t )  (2) 1 / 2  exp[i( p x x  Et) / ] ( p x )dp x (6.6)


which describes a localized free particle moving in one dimension is also a solution of the
equation (6.5). One can easily check , using Eq.(6.5), that

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

i  ( x, t )  (2) 1 / 2  E ( p x ) exp[i ( p x x  Et ) / ] ( p x )dp x
t 

p x2
 (2) 1 / 2  2m exp([i( p x x  Et) / ] ( p x ) dp x

(6.7)

2  2
  ( x, t )
2m x 2

The wave equation (6.5) is the time-dependent Schrodinger equation describing the
motion of a free particle in one dimension. Here it is important to remember that the total
 
energy E is represented by the operator E  i and the component p x of the
t
 
momentum by the operator p x  i . Equivalently, we can express Eq.(6.5) in the
x
operator form as

 1  2
E ( x, t )  ( p x )  ( x, t ) (6.8)
2m

This is how the classical relation (6.2) is represented in the quantum mechanical form.
Note also that Eq.(6.5) is of first order in time derivative  / t . Therefore, if the
wavefunction is given at a time t 0 , it can be determined at all other times with the help of
this equation.

3.2 Generalization to three dimensions

It is straightforward to generalize these considerations to three dimensions to

describe the motion of a free particle. Thus, a free particle of mass m and well defined

momentum p and energy E is now described by a plane wave

 
(r , t )  A exp(i(k .r   t ))
 (6.9)
 A exp[i( p.r  Et) / ]
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 
where the wave vector k  p /  and the angular frequency   E /  , which are related as
   k 2 /(2m) and satisfying the classical relation

p2
E (6.10)
2m

One can easily verify that the plane wave (6.9) now satisfies the partial differential
equation

  2 2 
i (r , t )    (r , t ) , (6.11)
t 2m

2 2 2
where  2
  (6.12)
 x 2 y 2 z 2

is the Laplacian operator. Eq.(6.11) is the three dimensional representation of

Schrodinger equation for a free particle having momentum p and energy E. In wave
mechanics, the total energy E and momentum p are represented by the differential
operators

   
E  i , p  i (6.13)
t

In operator form, the Schrodinger equation (6.11) is expressed as

  1  2 
E ( r , t )  ( p )  (r , t ) (6.14)
2m

Note that
 
( p) 2 /(2m)  2 /(2m)  2  T (6.15)

is, in fact the kinetic energy operator T of the particle.

The free particle Schrodinger equation (6.11) can now be generalized to the case of a

particle moving in a field of force. Here let us assume that the force F (r , t ) acting on the

particle can be derived from a potential V (r , t ) such that
  
F (r , t )  V (r , t ) (6.16)

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In this case, for a classical particle the total energy is given by the sum of kinetic energy
and its potential energy, viz.,

p2 
E  V (r , t ) (6.17)
2m

Since the potential energy V is independent of the momentum p or the energy E, we can
generalize Eq.(6.13) to write

   ( p) 2   
E(r , t )    V (r , t )  (r , t ) (6.18)
 2m 

so that the free particle Schrodinger equation (6.11) is now generalized to

   2 2   
i (r , t )     V (r , t )  (r , t ) (6.19)
t  2m 

This is the well-known time dependent Schrodinger wave equation proposed by

Schrodinger to describe the motion of a particle moving in a potential V. This is the
basic equation of non-relativistic quantum mechanics, which we should point out, can not
be proved like Newton’s laws in classical mechanics. In the treatment presented, we have
only tried to make it plausible. In fact, as we shall see in the subsequent study, the
successful application of Schrodinger equation to a variety of problems and the
comparison of its predictions with experimental data which demonstrates its correctness
in non-relativistic quantum mechanics.

In Eq.(6.19), the operator appearing in the bracket on the right hand side, is identified
as the Hamiltonian operator of the particle:

 2 2 
H    V (r , t )
2m (6.20)
1  2 
 ( p)  V  T  V
2m

Thus, in terms of the Hamiltonian, the time dependent Schrodinger equation is rewritten
as

   
H  ( r , t )  i  ( r , t ) (6.21)
t

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Let us recall that in classical mechanics, we describe the motion of a classical particle
moving in a potential given by

 p2 
E  H cl (r , p, t )   V (r , t ) (6.22)
2m

On comparison with Eq.(6.20), we find that quantum mechanical Hamiltonian operator is

  
obtained from the classical Hamiltonian, if we replace p  p  i , i.e.,
  
H  H cl (r ,i, t ) (6.23)

This shows quantum mechanical Schrodinger equation (6.21) may be obtained from the
classical equation (6.22) by the substitutions:

    
E  E  i , p  p  i (6.24)
t
   
and apply the operators E and H  H cl (r ,i) on both sides of the equation to the

wave function (r , t ) . Thus the analogy with classical mechanics as required by
correspondence principle becomes more apparent.

4. Conservation of Probability and Continuity Equation

We have seen in an earlier module that the wave function associated with a particle
in quantum mechanics has a statistical interpretation. According to Bohr’s postulate, if a

particle is described by a wave unction, (r , t ) ,normalized to unity, the probability of

finding the particle at time t within the volume element dr  dx dy dz about the point

r =(x,y,z) is

   2 
P(r , t ) dr   (r , t ) dr (6.25)

 
so that P( r ,t)=  ( r , t ) 2 represents the probability density. If the particle is confined
within a given volume, then at any arbitrary time t, the wave function can be chosen to
satisfy the normalization condition,
 2 
  (r , t ) dr  1 , (6.26)
where the integral extends over all space.

4.1 Probability conservation and the Hermiticity of the Hamiltonian

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Let us ask how does the probability density change with time ? The interpretation
 2
of  ( r , t ) as position probability density requires that the probability of finding the
particle somewhere in the space enclosed must remain unity as time changes., that is to

say that probability is conserved. Once  (r , t ) is normalized according to Eq.(6.26 ) it
must remain the same at all times. Therefore, the normalization integral must be
independent of time:
  
t  P(r , t ) dr  0 (6.27)

This condition, requiring the conservation in time of the normalization of the wave
function also implies that the Hamiltonian Eq.(6.20) of a particle in a real potential

V (r , t ) is a Hermitian operator.
To show this, let us write

     2
t  P ( r , t ) dr    ( r , t )
t
         
          dr (6.28)
  t   t  
   

 (i) 1 [  ( H )  ( H ) ] dr

So that condition, Eq.(6.27), reduces to
   
 ( H )d r   ( H )  d r (6.29)

which requires the Hamiltonian to be Hermitian. This condition must hold for all square

integrable wave functions  (r , t ) .Operators which satisfy the condition (6.29)
for all functions  of the function space in which they act are called Hermitian
operators.

4.2 Probability current density

To verify that relation, Eq.(6.27), is indeed satisfied in Schrodinger’s theory, we

write

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     2
t  P(r , t ) dr    (r , t )
t
   (6.30)
      
         dr
  t
    t  


Now, for the time dependence of the wave function  (r , t ) , let us employ the time-
dependent Schrodinger equation (6.19) and its complex conjugate

   2 2    
 i  (r , t )     (r , t )  V (r , t )  (r , t ) (6.31)
t 2m

(assuming the potential V (r , t ) to be real), we write
   i 
 P(r , t ) d r   [  ( 2 )  ( 2  ) ] d r
t 2m
V V
i 
  .{  ( )  (  ) } dr , (6.32)
2m
V
 
   . j dr
V
where in the last step, we introduce the current density vector,

   
j (r , t )  [  ( )  (  ) ] (6.33)
2i m

Eq.(6.30) can thus be expressed as

    
   t P ( r , t )  . jd r  0

(6.34)
V
where the integrand, for any finite volume, is zero. We thus get

  
P(r , t )  . j  0 . (6.35)
t
This is the continuity equation, analogous to the one we encounter in hydrodynamics
expressing the conservation of matter or in electrodynamics expressing charge
conservation. Just as in hydrodynamics, the continuity equation implies that no sources or
sinks of matter are present, in the same way, Eqn.(6.35) asserts that there is no creation or
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destruction of probability: any increase or decrease in the probability density is

compensated by the corresponding decrease or increase through an inflow or outflow of

probability ( . j ) d dt cross the boundaries of d .
Note that the probability current density, Eq.(6.33), can also be expressed as

    
j (r , t )  Re    
 i m  (6.36)
   
Since the operator  represents the quantity p / m , we can see that j corresponds to
im

the product of velocity and the density. That is why one can interpret j as a probability
current density.
We can convert the volume integral in the last part of Eq.(6.34) on the left hand side
into the surface integral S, enclosing the volume V by using Gauss’s divergence theorem
and get
   
 . j d r   j .dS (6.37)
V S

where dS is a vector whose direction is along the outward normal to the surface area
dS. The above relations hold for any finite volume. Note that to study the time rate of
change of the normalization integral, Eq.(6.26), we have to extend the volume to the
entire space. Consequently, the surface S in Eq.(6.37) then approaches to infinity, and
since ψ is square- integrable, it vanishes at large distances so that the surface integral in
Eq.(6.37) is zero. This is how condition, Eq.(6.27) is fulfilled. Hence the normalization
given by Eq.(6.26) is satisfied.

Example 2: for Probability Density and Probability Current of a Plane Wave:

Expressions
Suppose we consider a wave function of the form:
 
 (r , t )  N exp(ik .r  i t )

2 k 2
where   . The corresponding probability density
2m
 
P(r , t )   (r .t )  N
2 2

is uniform throughout all space and does not depend on tine. Using the expression for the current

sensity, the calculations of j ( r , t ) give

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 2 k 
j (r , t )  N  P (r , t ) vG ,l
m

k
where vG  represents group velocity associated with the momentum. We see that the
m
probability current is equal to the product of the probability density and the group velocity of the
particle. Both position probability density and the current density are time independent.

Example: Probability Density and Probability Current of a Plane Wave:

Expressions
Suppose we consider a wave function of the form:
 
 (r , t )  N exp(ik .r  i t )

2 k 2
where   . The corresponding probability density
2m
 
P(r , t )   (r .t )  N
2 2

is uniform throughout all space and does not depend on tine. Using the expression for the

current density, the calculations of j (r , t ) give

 2 k 
j (r , t )  N  P (r , t ) vG ,l
m

k
where vG  represents group velocity associated with the momentum. We see that
m
the probability current is equal to the product of the probability density and the group
velocity of the particle. Both position probability density and the current density are time
independent.

5. Admissibility Conditions on the Wave Function

To address the question as to what kinds of mathematical functions are

acceptable as wave functions for a particle in quantum mechanics, we find that the
probability interpretation of the wave function makes it necessary that  must satisfy
certain general criteria. In order to ensure that  d for an infinitesimal volume
2

element d should lie between 0 and 1 , we require that  should be (i) finite and
(ii)single valued . Single-valuedness is the requirement that at any point the wave
function should have a unique value so that the probability should not only be finite but

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also uniquely defined. Another property which is required of the wave function is that
  
 and its partial derivatives , and should be continuous functions of r for
x y z
all values of r. This requirement arises from the fact that the potential function is
supposed to be a continuous function of r except perhaps for a certain number of finite
discontinuities. This condition is therefore necessary for the consistency of the
Schrodinger equation .

6. Summary
After having studied this module you will be able to

 Learn how to develop the time dependent Schrodinger equation for a free particle
also for a particle moving in a field of force
 Know the three dimensional generalization of Schrodinger equation
 Learn to express the Schrodinger equation in operator form
 Learn how the normalization condition on the wave function leads to conservation
of probability and continuity equation.
 Know the admissibility criteria required for the Schrodinger wave function

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