114 Concept of wavefunctions

CHAPTER

6
Concept of Wavefunctions

Introduction :
Quantum mechanics acknowledges the wave-particle duality of matter and the existence of quantization by
supposing that, rather than travelling along a definite path, a particle is distributed through space like a wave.
The mathematical representation of the wave that in quantum mechanics replaces the classical concept of
trajectory is called a wavefunction,   (psi). The Schrodinger equation is a second-order differential equa-
tion used to calculate the wavefunction of a system.

SCHRODINGER’S WAVE MECHANICS

Consider a stationary wave associated with a microscope particle (e.g. electron) travelling in the x-direction
with precisely known momentum px and the total energy E. The wave equation of this stationary wave in terms
of coordinate x is given by
 2x 
  A sin   ... (1)
  
where  = wave function
x = Displacement of wave x-axis.
A = Amplitude of wave
 = wavelength of the wave
On double differentitation of equation (1) w.r.t x we get
d2 4 2  2x 
2
  2 
A sin  ... (2)
dx    
From equations (1) and (2)
d2 42
  ... (3)
dx 2 2
According to de Broglie’s equation.
h h
  [v = velocity of particle along x-axis]
p x mv

2 h2
  2 2
m v
 Equation (3) becomes
Concept of wavefunctions 115

d 2 42 2 2 42 m 2 v 2
 .m v  . ... (4)
dx 2 h2 h2

Now total energy = K.E. + P.E.

1 1
E mv 2  V  potential energy  ; mv 2   E  V  ; mv 2  2  E  V 
2 2
m2 v2  2  E  V  m ... (5)
From equation (4) and (5)
2
d 2  8 m  E  V 
 .
dx 2 h2
2
d 2  8 m  E  V 
Or  .  0 ... (6)
dx 2 h2
This is schrodinger’s wave equation for wave moving in one-dimension (x-axis). If the particle is moving
in 3-D space. (x, y, z, axes) then equation(6) becomes,
2
 2  2  2 8 m  E  V 
   .  0 ... (7)
x 2 y 2 z 2 h2

 2 2 2 
Since  2 =Laplacian operator =   
 x 2 y 2 z 2 
 
So, from equation (7)

82m
 2  E  V   0 ... (8)
h2
(I) Hamiltonian operator form of schrodinger’s wave equation:
From equation (8)

2 82 m 2 82 m 82mV

   2  E  v    0     2 E.  0
h h h2
82 mV 82 mE
  2     . ... (9)
h2 h2
 8 2 m 
Dividing by  2  in equation (9), we get
 h 

h2 h2  2 h2 
2 2
 . 2  V.  E   . 2  V.  E    . 82 m  V    E
8 m 8 m  

H  E ... (10)

 2 h2 
Where, H  
   V  called Hamiltonian operator and E = Eigen value.
 8 2 m 
116 Concept of wavefunctions

Equation (10) is called Schrodinger’s wave equation in the Hamitonian operator form.
For one-dimensional systems.
 2 d 2
  V  x   E
2m dx 2
where V(x) is the potential energy of the particle and E is its total energy. For three-dimensional systems.
2 2
    V  E
2m
where V may depend on position and 2 (del square) is
2 2 2
2   
x 2 y 2 z 2
In the general case the Schrodinger equation is written
Ĥ  E
where Ĥ is the hamiltonian operator for the system:
2 2
Hˆ    V
2m
For the evolution of a system with time, it is necessary to solve the time-dependent Schrodinger equation:

Ĥ  i
t
A central principle of quantum mechanics is that the wavefunction contains all the dynamical information about
the system it describes. Here we concentrate on the information it carries about the location of the particle.
The interpretation of the wavefunction in terms of the location of the particle is based on a suggestion
made by Max Born. He made use of an analogy with the wave theory of light, in which the square of the
amplitude of an electromagnetic wave in a region is interpreted as its intensity and therefore (in quantum terms)
as a measure of the probability of finding a photon present in the region. The Born interpretation of the
wavefunction focuses on the square of the wavefunction.
If the wavefunction of a particle has the value   x  at some point x, then the probability of finding the
2
particle between x and (x + dx) is proportional to  x dx .
2
Thus,  x is the probability density, and to obtain the probability it must be multiplied by the length of

the infinitesimal region dx. The wavefunction   x  itself is called the probability amplitude.
For a particle free to move in three dimensions (for example, an electron near a nucleus in an atom), the
wavefunction depends on the point ‘r’ with coordinates x, y and z, and the interpretation of   r  is as follows.
If the wavefunction of a particle has the value  at some point ‘r’, then the probability of finding the particle in
2
an infinitesimal volume d  dxdydz at that point is proportional to  d .
The square of a wavefunction is a probability density, and (in three dimensions) has the dimensions of
1/length3. It becomes a (unitless) probability when multiplied by a volume. In general, we have to take the
account the variation of the amplitude of the wavefunction over the volume of interest, but here we are suppos-
ing that the volume is so small that the variation of  in the region can be ignored.
Mathematical feature of the Schrodinger equation is that, if  is a solution, then so is N , where N
is any constant. This freedom to vary the wavefunction by a constant factor means that it is always possible to
find a normalization constant, N, such that the proportionality of the Born interpretation becomes an equality.
Concept of wavefunctions 117

We find the normalization constant by noting that, for a normalized wavefunction N the probability
that a particle is in the region dx is equal to  N  N  dx (we are taking N to be real). Furthermore, the sum
over all space of these individual probabilities must be 1.
The integration is over all the space accessible to the particle. For systems with spherical symmetry it is best to
work in spherical polar coordinates r ,  and  .
x  r sin  cos  , y  r sin  sin  , z  r cos 
r, the radius, ranges from 0 to 
 , the colatitude, ranges from 0 to 
 , the azimuth, ranges from 0 to 2
Standard manipulation then yield.
d  r 2 sin  drd d
Interpretation of the  functions:
The eigenfunction  is by nature a sort of amplitude function. In the case of a light wave, the intensity
of the light or energy of the electromagnetic field at any point is proportional to the square of the amplitude of
the wave at that point. From the point of view of the photon picture, the more intense the light at any place, the
more photons are falling on that place. This fact can be expressed in another way by saying that the greater is
the probability of a photon being within that region.
It is this interpretation that is most useful when applied to the eigenfunctions of Schrodinger’s equation.
They are therefore sometimes called probability amplitude functions. If   x  is a solution of the wave
equation for an electron, then the probability of finding the electron within the range from x to x + dx is given
2
by  dx .
The physical interpretation of the eigenfunction as a probability amplitude function is reflected in certain
mathematical conditions that it must obey. It is required that   x  be single-valued, finite, and continuous for
all physically possible values of x must have one and only one value. It cannot be infinite at any point, for then
the electron would be fixed at exactly that point, which would be inconsistent with the wave properties. The
requirement of continuity is helpful in the selection of physically reasonable solutions for the wave equation.
Since the function  may be a complex quantity, the probability is written more generally as  * ,
where  * is the complex conjugate of  . Thus, e.g., if   eix ,  *  eix .
The probabilistics nature of quantum mechanics disturbed many physicists, including Einstein, Schrodinger,
and de-Broglie, (Einstein wrote in 1926: “Quantum mechanics says a lot, but does not really bring us any closer
to the secret of the Old One. I, at any rate, am convinced that he does not throw dice.” When someone pointed
out to Einstein that Einstein himself had introduced probability into quantum theory when he interpreted a light
wave’s intensity in each small region of space as being proportional to the probability of finding a photon in that
region, Einstein replied, “ A good joke should not repeated too often”. These scientists believed that quantum
mechanics does not furnish a complete description of physical reality. However, attempts to replace quantum
mechanics by an underlying deterministics theory have failed. There appears to be a fundamental randomness
in nature at the microscopic level.
The Born interpretation puts several restrictions on the acceptability of wavefunctions. The principal
constraint is that  must not be infinite anywhere. (in other words,  would not be square-integrable) the
normalization constant would be zero. The normalized function would then be zero everywhere, except where
it is infinite, which would be unacceptable. The requirement that  is finite everywhere rules out many possible
solutions of the Schrodinger equation, because many mathematically acceptable solutions rise to infinity and
are therefore physically unacceptable.
118 Concept of wavefunctions

The requirement that  is finite everywhere is not the only restriction implied by the Born interpreta-
tion. A solution of the Schrodinger equation that gives rise to more than one value of function at a single point is
not accetable.
The Born interpretation implies that such solutions are unacceptable, because it would be absurd to
have more than one probability that a particle is at the same point. This restriction is expressed by saying that
the wavefunction must be single-valued; that have only one value at each point of space.
The Schrodinger equation itself also implies some mathematical restrictions on the type of functions
that will occur. Because it is a second-order differential equation, the second derivative of  must be well-
defined if the equation is to be applicable everywhere. We can take the second derivative of a function only if
it is continuous.
At this stage we see that  must be :
• Continuous
• Have a continuous slope
• Be a single-valued
• Should be finite.
A particle may posses only certain energies, for otherwise its wavefunction would be physically
unaccetable. That is, as a consequence of the restriction on its wavefunction, the energy of a particle is quan-
tized.

x=a x=a
(a) (b) (d)
The wavefunction must satisfy stringent conditions for it to be acceptable.
(a) Unacceptable because it is not continuous, at x = a
(b) Unacceptable because its slope is discontinous at x = a
(c) Unacceptable because it is not single-valued.
(d) Unacceptable because it is infinite at x = 0
We have claimed that a wavefunction contains all the information it is possible to obtain about the
dynamical properties of the particle (for example, its location and momentum). We have seen that the
Born interpretation tells us much as we can know about location, but how do we find any additional
dynamical information.

Quantum Mechanical Postulates

Postulate 1 :

The state of a quantum mechanical system is completely specified by a function   r , t  that depends on the
coordinates of the particle(s) and on time. This function, called the wave function or state function, has the
 
important property that  *  r , t   r , t  d is the probability that the particle lies in the volume element

d located at r at time t .
The wave function must satisfy certain mathematical conditions because of this probabilistic interpretation. For
the case of a single particle, the probability of finding it somewhere is 1, so that we have the normalization
condition

*  
   r , t   r , t  d  1


It is customary to also normalize many-particle wave functions to 1. The wave function must also be single-
valued, continuous, and finite.
Concept of wavefunctions 119
Postulate 2.
To every observable in classical mechanics there corresponds a linear, Hermitian operator in quantummechanics.
Postulate 3.
In any measurement of the observable associated with operator  , the only values that will ever be observed
are the eigenvalues a , which satisfy the eigenvalue equation
Â  a
This postulate captures the central point of quantum mechanics,the values of dynamical variables canbe quantized
(although it is still possible to have a continuum of eigenvalues in the case of unbound states). If the system is in
an eigenstate of  with eigenvalue a, then any measurement of the quantity A will yield a.
An arbitrary state can be expanded in the complete set of eigenvectors of i.e. Aˆ i  ai i as

   ci i
i

In this case we only know that the measurement of A will yield one of the values, but we don’t know which one.
2
However, we do know the probability that eigenvalue ai will occur is ci

An important second half of the third postulate is that, after measurement of  yields some eigenvalue ai , the
wave function immediately collapses into the corresponding eigenstate
Postulate 4.
If a system is in a state described by a normalized wave function  , then the average value of the observable
corresponding to  is given by


A    * Aˆ  d


Postulate 5.
The wavefunction or state function of a system evolves in time according to the time-dependent Schrödinger
equation
 
Hˆ   r , t   i
t
Probability :
Probability of finding a particle within a limit from lower limit to upper limit may be calculated as:
U,L
 *    must be normalised 
L,L

Normalisation
Normalisation means to bring a function in normal state. If a wave function satisfy this equation.

*
  d  1,

then it is said to be normalised.

The limits   and   are conventionally used to represent “all space”, although the entire space of a
system may not actually extend to infinitely in both directions. The integral’s limits would be modified to
represent the limits of the space a particle inhabits. Wavefunctions must be multiplied by some constant
so that the area under the curve of    is equal to 1. According to the Born interpretation of  ,
normalization also guarantees that the probability of a particle existing in all space is 100%.
 120 Concept of wavefunctions

In quantum mechanics,  that is obtained by solving wave equation is known as normalised wave func-
tion (vary often or generally). We deal here with the mathematical machinery needed to study quantum
mechanics.
We know that it is possible to multiply  by a constant A to give a new wave funciton, A , which is also
a solution of wave equation, now the problem is to choose the proper value of A, such that the new wave
function is a normalised function in order that it is a normalised wave function, it must meet the require-
ment
 
*
  A   A  d  1  A2   * d  1
 

1
 A 
where A is normalisation constant.
*
   d


SOLVED PROBLEMS
a
1. Calculate the probability that a particle in a 1-D box of length a is found to be between 0 and
2
2 n x
Soln. Normalised wave function for 1-D box is   sin
a a
a
2
Therefore, Probability    * dx
0

* 2 n x
For 1-D box;     sin
a a
 2n x 
 
2
1  cos  dx
2
a
2 n x a
2 2 2 n x 2 2a
a
 probability    sin  dx   sin dx  .0
0
 a a  0 a a a 2
a
 2n x  2
sin
2 a2 1 2 1 a2 2n x 2 a 1  a  0
  dx  cos dx   x  2

a 0 2 a 2 0 a 2a 0 a 2n
a
1 1 a  2n a  1 1 1
 
2 a 2a n sin 2a  sin 0   2  2an sin n  sin 0  2

2. An electron is trapped in 1-D region of length 1.0  10 10 m . In the ground state what is the probability of
finding an electron in the region x1  0.09  1010 to x 2  0.110  10 10 .
Soln. For ground state of 1-D box n = 1, First excited state of 1-D box n = 2
 sin x.sin x dx 
2 n x 2 n x U .L  
 sin  
*
sin *
 probability  L. L   dx  2

       sin xdx 

2 x
x2 2 n x 2 n x 2 x2 2 n x 2 x2 2  x 1  cos
 sin . sin dx   sin .dx   sin dx  2 2x
 dx
x1      x1   x1  
 1
x 2
Concept of wavefunctions 121
x2
 2 x 
sin
1 x 1   2 x2 2  x1 
2 x2 1 2 x2 1 2 x   x  2    1 1 
  dx   cos dx  x1   2     x2  x1   2  sin

 sin
 

 x1 2  x1 2  
   x1

1  2  0.110  10  2  0.09  1010  

10
 0.110  0.09 1010 sin 
   sin
1.0 1010 2  11010 1 1010 

1
 0.02  0.637  0.536  0.004  0.40%
2  3.14
3. In the first excited state, what is the probability of finding a electron between x = 0 and x  0.250  1010 m in
1Å box.
2 nx
Soln.   sin (for 1-D box)
 
Here first excited state is cosidered, so n =2
2 2 x * 2 2 x
  sin ,  sin
   
x2
 Probability of finding =   * d
x1

x
x 2 2 x 2 2 x  2 sin 2 2 x dx
 0
 sin sin dx
0     

 4 x 
x x 1  cos x
 dx  1 dx  1 cos 4 x dx  1 x  1 . 
x
 2 2 x  4 x  1  sin 4 x 
 where,  sin dx   sin    2 x  8
2 0 2

 0
 0
2  2 2 4  0  
 

2  x  sin 4 x 
 
  2 8  

x 1 4 x
  sin
 4 
0.250  1010 1 4  0.25 1010
  sin
1.0 1010 4 1.0 1010
1 1 1 1
  sin    0 
4 4 4 4
4. The probability of finding the particle in a one dimensional box of length L in the region between L/4 and
3L/4 for quantum number n = 1 is
1 1 1 1 1 2
(a) (b)  (c)  (d)
2 2  2  3
2 n x
Soln. Given that,   sin
 
 122 Concept of wavefunctions

3 /4 2 n x 2 n x
  sin sin
 /4    
2 3 / 4 2 n x n
 sin  a
  / 4  
2 3 / 4 2 3 / 4 1  cos 2ax 
  dx
  / 4 
 sin 2ax
  / 4 2 
3 /4
2  3 /4 3 / 4 1  3 / 4  sin 2ax  
  1dx   cos 2axdx    x   

2   /4  / 4     /4  2a   / 4 

1  3   1  3 2a.  
       sin 2a  sin 
  4 4  2a  4 2  
1   1  3a a   1 1  n n   
    sin  sin       sin    sin 
  4 2a  2 2    2 2a  4  2  

1  1 1  3n n  
    sin  sin  [For ground state n = 1]
   2a  2 2  

1   1  3  
    sin  sin  
  2 2a  2 2 

1  1 
    sin 270º  sin 90º   sin 270º  sin 180º 90º    sin 90º  1
  2 2a 
1  1 
     sin 90º  sin 90º  
  2 2a 

 
1  1 1  1 1   1 
     1  1 
   1  1  
   2    1    1 .   1  1
  2 2a 
   2 2a 
   2 n   2  n 2 
  
Correct answer is (b)
n x
5. A wave funtion given by   sin  0  x    is it normalised ? If not, normalise it.

  
n x 
Soln.
*
  dx   sin
2
dx   *
  dx  1
0 0  2 0

So, the function is not normalised.

To normalise this wave function, a constant A is taken with the function  and now function becomes
 A    '
So, according to the condition of normalisation,
  

 ' ' d  1   ' dx  1   A2 2 d x  1

2

0 0 0
Concept of wavefunctions 123

1 1 2
 A 
 
2

2 
 dx
0

2 n x
Therefore, normalised function =  sin
 
x
6. A particle is confined -a to +a and gives a wavefunction cos . Is it normalised? If not, normalise it.
2a
a a
* x x
   d 
a
 cos 2a cos 2a dx
a

a
2 x  2 1  cos 2 
  cos dx   cos   
a
2a  2 
x a a a
a 1  cos 1 1 x 1 a 1 a   x 
 a dx   dx   cos dx   x   sin 

a 2 2 a 2 a a 2  a 2   a  a

1 1 a a   a   1 a
  a   a    sin  sin   2a  sin   sin    
2 2 a a  2 2 
a
a sin   sin    sin   x    sin x 
2
2a sin 
a  a0 a
2
Therefore, function is not normalised.
To be normalised,  '  A 
a a
1 1
  A * A dx  1  A2 *
   dx  1  A a 
a a * a

a
 dx

Normalised wave function  1 cos  x .

a 2a
7. Which of the following functions are ‘well behaved’ quantum mechanically? [BHU-2015]
2
(a) exp( ax ) (b) exp(  ax) (c) x 2 (d) x
Soln. For well behaved function, function must vanish at  .
exp( ax 2 ) at x   exp( a 2 )  0

at x   exp( a2 )  0
Correct option is (a)
 124 Concept of wavefunctions

8. Which one of the following functions is quantum mechanically not acceptable? [BHU 2018]
(a) exp kx  
2
(b) exp  ikx  
(c) exp  kx
2
 (d) exp  kx 
Soln. For quantum mechanically acceptable wave function must vanish at  .

at x  ,    
  exp(kx 2 )  Not acceptable wave function
at x  ,    

at x  ,    
  exp( kx)  Not acceptable wave function
at x  ,   0 
Correct option is (a, d)
2
9. Consider the following functions: e x , eix , e  x and sin x. Which one of the following statements is true?
2
x ix
(a) e and e are even functions [HCU-2014]
(b) sin x is the only periodic functions in the list
(c) e  x and sin x are odd functions
(d) eix is a periodic function
Soln. eix  cos x  i sin x
So eix is periodic function
Correct option is (d)
10. Which of the following functions are acceptable as a wave function over the indicated intervals?
2
(a) e  x  ,   (b) e  x  ,   (c) e x  0,   (d) sin 1 x  1,1 [DU 2017]
Soln. For an acceptable wave function, wave function must vanish at boundary
(a) at x  ,   e| x|  e||  e   0

at x  ,   e | x|  e ||  e   0

  e |x| acceptable wave function

2
(b)   e  x
2
at x  ,   e (  )  e   0
2
at x  ,   e  (  )  e   0
2
  e x acceptable wave function
x
(c)   e
at x  0,   e  x  e0  1

at x  ,   e   0

  e  x not acceptable wave function as wave function does not vanish at x  0

1
(d)   sin x
Concept of wavefunctions 125

at x  1,   sin 1 (1)  sin 1 (sin )  

  
at x  1,   sin 1 (1)  sin 1  sin  
 2 2

  sin 1 x, not acceptable wave function as wave function does not vanish at x  1 and x  1 .
Correct options are (a, b)
11. The ground state of a harmonic oscillator has number of nodes [DU 2018]
(a) 2 (b) 0 (c) 1 (d) 3
Soln. Wave function of harmonic oscillator in the ground state is given by

1/4
 2
 0    e x
 

(x)

Ground state wave function of harmonic oscillator has zero node.

Correct option is (b)
12. Indicate which of the following is/are “acceptable” wave function(s) in quantum mechanics in the range
x [TIFR 2015]
i. x ii.   x 2 iii.   sin x iv.   exp (  x)
v.   exp(  x 2 )
(a) iii and v (b) iv only (c) iv and v (d) i and iii
Soln. Wave function should be finite and single-value every where in space
Above condition satisfied by   sin x and   exp( x 2 )
Correct option is (a)
13. Which of the following statement(s) is/are true ? [TIFR 2015]
(i) The state function (x, t) is always equal to a function of time multiplied by a function of the coordinates
(ii) I f f 1 and f2 are eigenfunctions of an operator B, then c1f1  c 2 f 2 must always be an eigenfunction of B,
where c1 and c2 are constants
(iii) The operator L2 commutes with Lx + Ly
(a) i and ii (b) i and iii (c) ii and iii (d) Only iii
Soln. [ Lˆ2 , Lˆx  Lˆ y ]  [ Lˆ2 , Lˆ x ]  [ Lˆ2 , Lˆ y ]  0  0  0
Correct option is (d)