____________________________________________________________________________________________________

Material science

Paper No. : Quantum Mechanics

Module : Time independent Schrodinger equation, Stationary
States & Energy Spectra

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
ofDelhi, 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 8 Time independent Schrodinger equation, Stationary states

& Energy Spectra
Module Tag V S Bhasin

TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. . The time- independent Schrodinger equation. Stationary states and

Energy Spectra

3.1 Energy Eigen values and eigenfunctions

3.1.1 Continuity Conditions

3.1.2 Energy Spectrum and Energy Eigen functions

3.2 A Particle in One- Dimensional Square Well Potential

3.2.1 The Energy Eigenvalues

3.2.2 The Energy Eigenfunctions; Parity

3.2.3 Penetration into Classically Forbidden Regions

4. Summary

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1. Learning Outcomes (Times New Roman , size 14)

After studying this module, you shall be able to

 Learn how to reduce the time-dependent Schrodinger equation into time

independent and time dependent parts and thus write the time independent
Schrodinger equation as an eigen value equation for energy eigenvalue and the
corresponding eigen functions
 Solve the time independent one-dimensional Schrodinger equation for an
attractive square well potential
 Find the discrete energy spectrum of a quantum mechanical particle and the
corresponding eigen functions
 Learn that for a potential which is symmetric about the origin, there exists even
and odd parity states
 Find a striking quantum mechanical feature of these eigenfunctions which show a
(non-zero) finite probability of the particle being outside the range of the potential

2. Introduction

In this module, we discuss the solutions of stationary states and energy spectra of
time-independent Schrodinger equation. We take a specific example of a square well
attractive potential and solve one-dimensional Schrodinger equations to obtain the
discrete spectrum of energy eigenvalues ( E<0) and the corresponding eigenfunctions.
Given the potential which is symmetric about x-axis, the energy eigen functions are
found to have definite parity states ( odd/ even). A striking feature of the wave function
of a quantum mechanical particle bound in a square well potential is that there exists a
(non-zero) finite probability of the particle being even outside the range of the potential.
This is in contrast to the classical case where the particle can strictly be confined within
the range of the potential.

3. The time- independent Schrodinger equation. Stationary states

and Energy Spectra

3.1 Energy Eigen values and eigenfunctions

Consider the particular case when potential energy V of the particle does not depend
on time. In such a case, the Schrodinger equation

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
 (r , t ) ˆ 
i  H (r , t ),
t (8.1)

where  
Hˆ   2 / 2m  2  V (r )

admits of considerable simplification. We can then write a particular solution of the form
 
(r , t )   (r ) f (t ) (8.2)

which is separable in space and time coordinates. We shall see that the general solution
can be expressed as a sum of such separable solutions. Substituting Eq.( 8.2) in Eq.(8.1 )
and applying the method of separation of variables, we have

 df (t )  2 2   
i (r )     (r )  V (r ) (r ) f (t ) (8.3)
dt  2m 
 
Dividing both sides of this equation by (r , t )   (r ) f (t ) , we get

1 df (t ) 1  2 2   
i      (r )  V (r ) (r ) (8.4)
f (t ) dt  (r )  2m 

Here we note that since the left hand side depends only on t and the right hand side only
on r , both sides must be equal to a constant. Since this constant has the dimensions of
energy, we denote it by E. We therefore get the two equations

df
i  E f (t ) (8.5)
dt
and
 2 2   
 2m   V (r ) (r )  E (r ) (8.6)
 

The first equation, on integration, gives

f (t )  C exp(iE t / ) (8.7)

where C is arbitrary constant. Since both the equations (8.5) and (8.6) are homogeneous
equations, we can, without loss of generality, put C=1 and write the solution Eq.(8.2) as

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 
(r , t )   (r ) exp(iE t / )
(8.8)


Applying the time-derivative operator i t to both sides, we get


 (r , t ) 
i  E ( r , t ) (8.9)
t

Equation (8.9)is called an eigen value equation;  is said to be an eigenfunction of the

operator appearing on the left and the constant E appearing on the right is called the
corresponding eigenvalue. Energy eigenfunction  represents the stationary state of the

particle, since  is constant in time. Eq.(8.6) for the function  (r ) is also an
2


eigenvalue equation. It states that  (r ) is an eigenfunction of the operator

 2 2 
   V (r )
 2m 

having the same eigenvalue E. Remembering that the Hamiltonian operator

ˆ     2  V (r)
2

of the particle is given by H   , we may this equation as an

 2m 
eigenvalue equation,viz.,

  2 2   
Hˆ  (r )     V (r )  (r )  E (r ) (8.10)
 2m 

We shall be discussing the significance of eigenfunctions and eigenvalues in the next

module. Her we assume that the energy eigenvalues E are the only possible results of the
precise measurements of the total energy of the particle. To show this, we first note that E
is real. Clearly, for the separable wave functions of the form Eq.(8.8), the position
probability density is
  
P( r , t )    (r , t )  (r , t )
   i  (8.11)
   (r ) (r ) exp  ( E  E) t 
  

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From the probability conservation and assuming that  is

square integrable, we get
  
( E  E  )    (r , t ) (r , t ) dr  0 (8.12)


Thus it follows that E  E and E is therefore real. We therefore state that the eigen
values E of time-independent Schrodinger equation (8.10) are real and also the
Hamiltonian is Hermitian as implied by the probability conservation.

Further, we find from the calculation of the expectation value of the total energy in a
state described by the wave function (8.8)

       
E     (r , t ) i   (r , t ) dr     (r , t ) Hˆ  (r , t ) dr
 t  (8.13)
E

In other words,

E H  T  V (8.14)

Here we assume that  is normalized to unity. We have thus shown the eigen values E
are the only possible results of the precise measurements corresponding to the
expectation value of the total energy in the state Eq.(8.8).

3.1.1 Continuity Conditions

Returning to time independent wave equation (8.10), we note that it is a second

order linear differential equation in r . Thus so long as V(r ) is finite, whether it is
continuous or not , a knowledge of the wave function and its gradient along a surface
makes it possible to integrate the equation to obtain the wave function at any point. It is,
therefore, reasonable to demand that the wave function and its derivative be continuous,
finite and single valued at every point in space so that a definite physical situation can
be represented uniquely by a wave function. These requirements will also ensure that the
position probability density and the probability current density earlier defined are
continuous everywhere.

3.1.2 Energy Spectrum and Energy Eigen functions

Looking for the solution of the energy eigenvalue in Eq.(8.10), the question that still
remains to be answered is : given any arbitrary real value for E, does there exist a

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
corresponding eigen function  E (r ) ? The answer is :No.
The reason is that Eq.(8.10) would satisfy the admissibility conditions only for certain
specific values of E. Only these special values are to be considered as eigenvalues. The
set of all such admissible values of E is called the eigenvalue spectrum of energy and the
corresponding wave functions are called the eigen functions. We shall consider a simple
system to illustrate how the

admissibility conditions on the wave functions lead to the restrictions on the possible
energy spectrum.

3.2 A Particle in One- Dimensional Square Well Potential:

Let us consider a particle whose potential energy function has the shape of a well
with vertical sides as depicted in Fig.(8.1)and is defined by:

V(x)=0 for x < -a ( Region I)

V(x)=- V0 for -a < x < a (Region II) (8.15)

V(x)=0 for x > a (Region III)

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Fig. 8.1 The square well potential

From the point of view of classical mechanics we know that the kinetic energy (E-V)
can never be negative. For the region x  a , the potential V=0, therefore , (E-V) will be
positive if E > 0; in other words, any particle with E < 0 cannot enter the regions I and III
and will have to stay within the potential ‘well’ between x=+a and x=-a, i.e., the particle
is said to be confined within the potential. If, however, the particle has energy E > 0, it
can move anywhere; it would experience momentary force when it crosses the point x=-a
and x=+a.

Let us now study the picture of this system from the point of view of quantum
mechanics. Considering only the stationary states described by the Eq.(8.10) and
restricting ourselves to one-dimensional case, the equation reduces to

2 d 2
  E , x a (8.16a)
2m dx 2

2 d 2
and  V0  E , x ,a (8.16b)
2m dx 2

To solve this set of equations, let us first consuder the case when E < 0 corresponding to
the case when the system is bound.

Bound States in Square Well: (E < 0)

(a) Admissible Solutions of Wave Equation:

For the case E < 0, let us write

2mE 2m( E V 0)
  2 and   2; ,   0 (8.17)
2 2

The Eqs. (8.16) can now be expressed in terms of the constants  2 and  2 as

d 2
  2 =0 for x  a (8.18a)
dx 2

d 2
2
  2  0 for x  a (8.18b)
dx

The general solution of the second equation is clearly

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 II ( x)  A cos  x  B sin  x (8.19)

where A and B are arbitrary constants. The superscript on  (x) indicates that this
solution is valid in the region II, i.e., for ( x  a . In region I, the general solution of
Eq.(8.18a) is a linear combination of two independent solutions exp(x) and exp(x)

However, in the region I, where x is negative the second solution does not remain finite;
as x   , it goes to infinity.Thus the only admissible solution in region I is of the form

 I ( x)  C exp( x) (8.20)

The region III which corresponds to (a < x <  ) has a solution also governed by the
Eq.(8.18a), which has two independent solutions exp(x) and exp(x) . But this time
it is exp   x) which is well behaved everywhere and the solution exp(  x) is no longer
admissible; it goes to infinity as x becomes infinitely large. We, therefore, have

 III ( x)  D exp(x) (8.21)

where C and D are the constants to be determined. We now require that the wave
functions and their derivatives in the three regions must be continuous everywhere as
demanded by the admissibility criteria mentioned in the earlier module. In particular, at
the point x=-a, where regions I and II meet, we require

d I d II
 I   II and  at x=-a, (8.22)
dx dx

or explicitly

C exp( a)  A cos  a  B sin a , C  exp( a)  A  sin  a  B  cos  a

(8.23)

Similarly, at x=a, where regions II and III meet, we have the conditions

d II d III
 II   III and  , ( x  a) (8.24)
dx dx

Written explicitly, these equations give

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D exp  a)  A cos(a)  B sin( a),

 D exp(  a)   A  sin(  a)  B cos( a)
(8.25)

Using Eqs.(8.23) and (8.25), we get

2 A cos( a)  (C  D) exp( a ) (8.26a)

2 A sin(  a)  (C  D)  exp(  a) (8.26b)
2 B sin(  a)  (C  D) exp(  a) (8.26c)
2 B cos( a )  (C  D)  exp(  a ) (8.26d )

From Eqs.(8.26), we find that if (C+D)  0, then A  0 and dividing (8.26b) by (8.26a)
we have

   tan  a (8.27a)

The next two equations show that for Eq.(8.27a) to be valid, we must have

C=D and B=0 (8.27b)

and hence D  A exp( a) cos(a) (8.27c)

To verify this, let us substitute Eq.(8.27a) for α in Eq.(8.26d) and then multiply the
equation by sin(βa) and using Eq.(8.26c) we obtain

 (C  D) cos2 (a)  (C  D) sin 2 ( a)

or (C  D) (cos2 a  sin 2  a)  0

clearly showing that C must be equal to D. On substituting this back in Eq.(8.26a) we get
Eq.(8.27c). Eqs. (8.27) give us one ste of solutions. Another set of solutions exist when

CD and B  0.

when we get from Eqs.(8.26c) and (8.26d)

   cot( a) (8.28a)

Repetition of the arguments given above show that now

C = -D and A = 0 (8.28b)

In this case, Eqs.(8.26) give

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D  B exp( a) sin(  a) (8.28c)

3.2.1 The Energy Eigenvalues

We shall now see that both types of the solutions obtained above give rise to
certain discrete values of the energy parameter. Let us first note that Eqn.(8.17) can be
simplified to

2mV0 a 2 V0
( 2   2 ) a 2   , (8.29)
2 
 2
where  (8.30)
2ma 2

The parameter Δ admits of an interesting interpretation. The potential well has half-width
a which indicates the uncertainty in the position of the particle confined to the well.
Associated with this there is an uncertainty of the order of (/ a) in the momentum.
Therefore, parameter Δ , corresponding to the energy ( / a) 2 /(2m) is a natural unit in
terms of which the depth of the potential may be measured. In other words, the
dimensionless parameter (V0 /  ) defined by Eq.(8.29) gives a measure of strength of the
potential.

Besides the relation, Eq.(8.29), we have also Eq.(8.27a) giving us the relation
between  and  ,which are defined to be positive. This shows that from the
equation ( /  )  tan a , only the values of  a , which lie in the intervals

 
2n   a  (2n  1) (n  0,1,2,..........) (8.31a)
2 2

are admissible. Also note the substitution of the relation    tan a into the Eq.(8.29)
leads to the result

V0
  2 a 2 sec 2 (  a)

1/ 2 (8.31b)

or    a  cos a
 V0 

The modulus sign is used because the left hand side of the equation is known to be
positive.

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Similarly for the second type of solutions of the wave equation, we find from
Eqs.(8.28a) and (8.29) that

 
(2n  1)   a  2n , (n  1,2, 3, ...........) (8.32a)
2 2
and
1/ 2
V0 
  2 a 2 cos ec 2  a ,    a  sin  a (8.32b)
  V0 

Equations (8.31) and (8.32) can be satisfied only by certain discrete values of β which
can be found graphically.

Fig. 8.2 Graphical solutions for allowed values of β a

These values of  r a are determined by the intersections of the straight line  / V0   a

1/ 2

with the curves for cos  a and sin  a . The parts of cos  a and sin  a
which lie within the respective allowed intervals -- conditions (8.31a) and (8.32a)—are
shown as red and green lines respectively in Fig.(8.2). If the intersections occur at    r
(r=0,1,2. .. … 0 the corresponding values of the energy are obtained from
Eqs.(8.17) as

2 2   
Er   r  V0   r a 2  1 V0 (8.33)
2m  V0 

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Note that the values of the combination of parameters appearing in the square bracket
may be read directly from the figure. Clearly the number of these energy levels is finite.
We can check from the figure that if  / V0   a reaches the value unity for a value of
1/ 2

1 1
β a in the interval N   a   ( N  1) , then there are (N+1) intersections. In other
2 2
word, the number of discrete energy is (N+1), if

1 1
N ( / V0 )1 / 2  1   ( N  1) ( / V0 )1 / 2 ,
2 2

1/ 2
2  V0 
0r if N (    ( N  1) (8.34)


Note that there is at least one bound state, however weak the potential is.

3.2.2 The Energy Eigenfunctions; Parity

We find that the energy levels E n with n=0, 2, 4, correspond to solutions

represented by Eqs.(8.27). For the three regions, the forms are explicitly written as

 nI ( x)  ( A e n a cos  n a) exp( n x) ( x  a)

 nII ( x)  A cos  n x (a  x  a) (8.35)
 nIII ( x)  ( Ae n a cos  n a) exp(  n x) ( x  a)

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These functions are shown graphically in Fig.(8.3a). Clearly these functions are
symmetric about the

origin.

Fig. (8.3a) Even parity eigenfunctions corresponding to quantum number n=0, 2, 4.

The eigen function , n = 0 is coloured green, n = 2 yellow and n= 4 violet. Note that
ground state eigen function has no node, whereas the state, n=2 has two nodes and the
state n=4 has 4 nodes. In general any wave function which is characterized by

 n ( x)   n (  x)

i.e., it remains symmetric for x going to (-x) is said to have even parity.

The eigen functions corresponding to n=1, 3, 5, …….are given by Eq.(8.28), which can
be explicitly written as

 nI ( x)   ( B e n a sin  n a) exp( n x) ( x  a)

 nII ( x)  B sin  n x (a  x  a)
 nIII ( x)  ( Be n a sin  n a) exp(  n x) ( x  a) (8.36)

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These functions are depicted in Fig.(8.3b).

Fig. (8.3b) Odd parity eigen functions corresponding to the quantum numbers n=1, 3, 5.

The state n=1 is coloured as violet, n=3 as orange and n=5 as green . These odd parity
states are antisymmetric under the interchange x going to –x, i.e.,

 n ( x)   n ( x)

The fact that the eigenfunctions have even or odd parity is a consequence of the
symmetry property of the potential V with respect to the origin. In one of the subsequent
modules we shall give definition of parity in the case of more general systems and
discuss the connection between the nature of potential and the parity states.

3.2.3 Penetration into Classically Forbidden Regions

From the figures (8.2) and (8.3), one can clearly notice that these bound state
eigen functions of a quantum mechanical particle have non-vanishing values and are
finite even outside the range of the potential. This shows that there exists a finite
probability for the particle to penetrate even outside the potential. This result is in striking
contrast to classical mechanics where the motion of the particle is strictly confined within
the given potential. From the bound state eigenfunctions  n (x ) given by Eqs.(8.35) and
(8.36) , it is simple to observe that as one goes from the boundary point ( x=-a or x=a) the
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probability density  (x) decrease rapidly proportional

2

to exp(-2  x ) to zero for large x . This provides an illustration of a quantum mechanical

feature of fundamental importance. Here we have so far considered the situation where
E< 0, i.e., all the states are bound. In the next module we shall discuss the case for E> 0,
where the energy spectrum is a continuum.

5. Summary

After having this module, you shall be able to

 Learn how to reduce the time-dependent Schrodinger equation into time

independent and time dependent parts and thus express the time independent
Schrodinger equation as an eigen value equation for energy eigenvalue and the
corresponding eigen functions
 Solve the time independent one-dimensional Schrodinger equation for an
attractive square well potential
 Find the discrete energy spectrum of a quantum mechanical particle and the
corresponding eigen functions
 Learn that for a potential which is symmetric about the origin, there exists even
and odd parity states
 Find a striking quantum mechanical feature of these eigenfunctions which show a
(non-zero) finite probability of the particle being outside the range of the potential

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