B.Sc.

CSIT physics Lecture-

9

R.R.Mahto
Bhaktapur M. Campus
Methods of Quantum Mechanics
Introduction

we have discussed some of the experimental evidence that

led to the breakdown of classical physics and to the
beginning of quantum mechanics. We have seen how the
introduction of the quantization postulates explained the
experimental facts concerning blackbody radiation, the
photoelectric effect, and the hydrogen spectrum. These
theories constitute the old quantum theory (OQT).

Despite its successes, the OQT has some serious deficiencies:

1.The theory can be applied only to periodic systems (harmonic
oscillators, circular motion, and such), although there are many
important physical systems that are not periodic.

2. Although the Bohr theory predicts the observed wavelengths of the

spectrum of hydrogen, it does not explain why certain wavelengths are
more intense than others; that is, it does not account for the rate of
transition between different energy levels.

3. The Bohr theory explains well the spectrum of monatomic hydrogen (H),
singly ionized helium (He+), and reasonably well those of the alkali
elements (Li, Na, K, . . . ), but It fails to explain the spectrum of even the
simplest of the multi electron atoms, He.

4. The most serious criticism of the OQT is that it is intellectually

unsatisfying; it is not a unified or a general theory. It assigns to microscopic
particles a well-defined path that, by the uncertainty principle, is not
possible.
THE SCHRODINGER THEORY OF QUANTUM
MECHANICS
The Time-dependent Schrodinger Equation

The basis of the modern theory of quantum mechanics

was developed in 1925 by Erwin Schrodinger (1887-1961);
In this we discuss about the behavior of a microscopic particle
is governed by the wave associated with it, according to de
Broglie's guideline. We can use a sinusoidal traveling wave,
that is, either

  A sin kx  t  Or,   A coskx  t 

or a linear combination of both.
The Schrodinger theory tells us how to obtain the wave
function  (x,t) associated with a particle, when we specify the
forces acting on the particle, by giving the potential energy
associated with the forces. The Schrodinger theory also tells
us how to extract information about the particle from the
associated wave function.

Schrodinger developed a differential equation whose

solutions yield the possible wave functions that can be
associated with a particle in a given physical situation. This
equation, known as the Schrodinger equation. when a
function depends on more than one independent variable, the
derivative of the function with respect to one of them, while
treating the other variables as constants, is called the partial
derivative with respect to that variable.
The total energy of a particle is equal to the kinetic
energy plus the potential energy,

1
E  mv 2  E p
2

p2
E  E p ……………..(1)
2m
Multiplying 1 both sides by 

p2
E    E p ……………..(2)
2m

Applying energy operator, E= iħ /t and momentum

operator, p = –iħ /x we get,
  1    
i    i   i   E p
t 2m  x  x 

  2  2
i   E p
t 2m x 2

Hence,
 2  2 
  E p  i ……………..(3)
2m x 2
t

Equ.3 is known as the one-dimensional time-dependent

Schrodinger equation. If the potential energy Ep is known,
this equation can be solved and the solution will yield the
possible wave functions that we can associate with the
particle.
  2  2 
  E p  i
2m x 2
t

Schrodinger Equation for a Free Particle

Let us consider a free particle moving along the x-axis with
momentum p = mv and energy E = 1/2mv2. If no force acts on
the particle (i.e. F = 0) then energy E = constant. It means EP = 0,
so the Schrodinger equation can be written as
 2  2 
  i ………………………………………..…....(1)
2m x 2
t
wave function of travelling wave is. either
  A sin kx  t  Or,   A coskx  t  ……..(2)
Differentiating this wave function 2 w.r.to x
 
 A sin kx  t   kAcoskx  t 
x x
 and the second differentiation yields
 2     
    kA coskx  t    k 2
A sin kx  t  …..(3)
x 2
x  x  x

Again differentiating this wave function 2 w.r.to t is

 
  A sin kx  t   A coskx  t  ……….…...(4)
t t
Substituting the values of equation 3 & 4 to equation 1, we
get


2
2m
 
 k 2 A sin kx  t   i A coskx  t 

2 2

A sin kx  t   iA coskx  t 
Or, k
2m
Because the sine and cosine functions are equal only for
certain angles (at 45°), this cannot be satisfied for all x's and
t's. Similar results are obtained with the cosine function.
There is, however, a particular combination of these two
functions that does satisfy the Schrodinger equation. This
combination is
  A coskx  t   iA sin kx  t 
i  kx t  …..………………………………………...(5)
Or,   Ae
Now we have to show that eqn. 5 satisfies the Schrodinger
equation by substituting into Eqn.1. For this ,differentiate Eqn.
5 twice with respect to x we get.



x x

 
Aei kx t   ikAei kx t 
  2     
And,    
x 2   x  x
ikAei  kx t 

 ik 2
Aei  kx t 

 2 i  kx t 
Or,   k 2
Ae
x 2
The derivative of 5 with respect to t yields

t


t
 
Aei kx t   iAei kx t 

and, substituting into Eq. 1, we get

 2  2 
   
2

  k 2 Aei kx t   i  iAei kx t    i
2m 2m x 2
t

 2k 2
Or,   …..………………………………………………..(6)
2m
which means that Eq. 5 is a solution for this relation of the
constants
We must now show that Eq. 5 is consistent with de Broglie's
hypothesis also. The kinetic energy of a particle is given by
E = 1/2mv2=p2/2m.
From de Broglie's hypothesis,

E  h  h  
2
And,
hh
p   k
 2
k
Substituting these relations into the expression for the
energy given below,
 p2
E
2m

Or,  
k 
2

 2k 2
2m 2m
 2 k 2 ………………………………………………....…..(7)
Or,  
2m
Eq.6 and 7 are same and the consistency of the formulation.
The wave function  that satisfies the Schrodinger equation
and de Broglie's postulate. But wave function in Eq. 5 is not a
real function. The wave function itself has no physical

2
meaning. But has physical significance.

   
2
 where * is the complex conjugate of .

     Ae

 Ae 
i kx t   i kx t 
 Aei kxt  Aei kx t 
2

  A A
2
Or,
This gives real quantity. In above equation, the probability of
finding the particle at any point in space is given by  dV and
2

therefore  2, properly normalized. The probability density

that must be both real and positive. P r , t dV  
2
dV
Num. 1. For free quantum particle show by direct distribution
it

that the wave function  x,t   A cos kxe satisfies the time-
dependent Schrödinger equation. For the free particle.
Ans.
We have the time dependent Schrödinger equation.

 2  2 
  i …………..…..(1)
2m x 2
t
The given wave function is,

  x,t   Acos kxeit

Now differentiating this wave function with respect to x is,

x


x
 
A cos kxeit  kAsin kxeit
Again,
 2     
x 2
   
x  x  x
 kA 
sin kxeit
 k 2
A cos kxeit

And differentiating the wave function w.r.to t we get,


t


t
 
A cos kxeit  iA cos kxeit

Substituting these values in 1 we get,


2
2m
  
 k 2 A cos kxeit  i  iA cos kxeit   2  2 
  i
2m x 2 t
 2k 2
Or,  
2m
Hence given wave function is the solution of time dependent
Schrödinger equation for free particle.
Num.2 Show by direct substitution into the time-
dependent Schrodinger equation for the free particle,
that ",   x ,t   A coskx  t  is not a solution.