SCHRODINGER EQUATION

THE WAVE FUNCTION:

 Each “particle”is represented by a wave function (x,t) such that *=the probability of finding
the particle at that position at that time
 The wave function is used in the Schrodinger equation. The Schrodinger equation plays the role
of Newton’s laws and conservation of energy in classical mechanics. It predicts analytically and
precisely the probability of events.

Wavefunction Properties

 contains all the measurable information about the particle

 * summed over all space=1(if particle exists, probability of finding it somewhere must be one

 and its derivative is continuous

 allows energy calculations via the Schrodinger equation

 permits calculation of expectation value of a given variable.

 is finite and single valued

SCHRODINGER’S EQUATION:

It is a fundamental of quantum mechanics similar to that of second law of motion of Newtonian

mechanics. It is a wave equation in the variable . In quantum mechanics the wave function 
corresponds to the wave variable y of wave motion. unlike y, is not itself a measurable quantity and is
therefore, complex.

TIME-DEPENDENT FORM:

Consider a particle moving freely in the +x direction. Let us assume a wave function for this particle .
The wave function forsuch particle may be represented as

  Aei (t  x / v ) .............(1)
Replacing ω = 2πʋ and velocity v = ʋλ

  Ae2 (t  x /  ) ............(2)

Also E = hν= 2 π  ν and λ = h/p = 2 π  /p where  = h/2πequation (2) can be rewritten as

  Ae(i /  )( Et  px) ..........(3)

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

Differentiating (3) for twice w r to x gives (partial derivative)

2 p2
 2  or
2 x2 

 2
p    2 2 ...........(4)
2 2

 x

Also differentiating (3) for once w r to t gives

 iE
 
t 

 
E   .................(5)
i t

The quantities
  
are called operators. p  i E
x i t

The total energy E of a particle is the sum of its kinetic energy and potential energy

p2
E  V ( x, t )............(6)
2m
Multiply (6) by on both sides gives
 p2
E   V..................(7)
2m

Substitute for E  and p2 to obtain the time dependent form of schrodinger equation:

 2 2
i   V....................(8)
t 2m x 2

This is the time dependent form of Schrodinger equation.

In three dimensions the time dependent form of Schrodinger’s equation is

 2   2  2  2 
i    2  2   V..............(9)
t 2m  x 2 y z 

Where the particle’s potential energy V is some function of x,y,z and t. Any restriction that may be
present on the particle’s motion will affect the potential energy and once V is known Schrodinger's
equation may be solved to obtain the energy, wave function and probability density of the particle.

EXPECTATION VALUES:

The average position of a number of particles distributed along the x axis such that N1 particles at x1,
N2 particles at x2 and so on is given by

N1 x1  N 2 x2  N3 x3  .....  Ni xi
X  .............(1)
N1  N 2  N3  ........  Ni
For a single particle the number Ni at xi must be replaced by the probability

Pi  i dx.........................(2)
2

Where i is the particle wave function evaluated at x=xi. Making substitution and changing the
summations to integrals, the expectation value of the position is given by
 

x
2
dx
x  

................................(3)

2
dx


If the wave function is normalized

then

i.e.   dx  1
2




x  x
2
dx.................................(4)


Similarly expectation values of momentum and energy are given by

 
p   p  dx E  E
2 2
dx......(5)
 

SCHRODINGER EQUATION: STEADY-STATE FORM

The wave function  of unrestricted particle may be written as the product of time dependent and
position dependent part as

  Ae(i /  )( Et px)  Ae(iE /  )t e (ip /  ) x

i.e.  e(iE /  )t ............................(1)
( small is a position dependent part  = e  (ip /  ) x )

is the product of time dependent and a position dependent function

Substituting  in time dependent form of Schrodinger equation

   2  2
i   V..........(2)
t 2m x 2

(Take partial derivative wrt x and t of eq (1) and put in (2) )

We get

 2 (iE /  )t  2
Ee ( iE /  ) t
 e  V e ( iE /  ) t

2m x 2

Dividing through by the common exponential factor gives

 2 2m
 ( E  V )  0....................(3)
x 2  2
is the steady-state form of Schrodinger equation.

In three dimensions the equation takes the form as

 2  2  2 2m
   ( E  V )  0........(4)
x 2 y 2 z 2  2
Importance/applications of Schrodinger equation in quantum mechanics:

EIGENVALUES AND EIGENFUNCTIONS:

Schrodinger equation can be solved for a given problem. It will have many solutions. Some solutions are
real, imaginary and complex. Their linear combination is also a solution. A proper or characteristics
solution of the equation which gives correct value of energy is called eigen function. And the value of
energy obtained from eigen function is called eigen value.

The values of energy En for which Schrodinger’s steady-state equation can be solved are called
eigenvalues and corresponding wave functions n are called eigenfunctions.

For example eigen functions and eigen values for a particle trapped in one dimensional box are as
under:

2 n n 2 2  2
n  sin x En  ..n  1,2,3,......
L L 2mL2
APPLICATION: PARTICLE IN A BOX

Aim: To show energy quantization and to learn

1.How to set and solve Schrodinger’s equation?

2.Obtain eigenvalues and eigenfunctions

3.Compare the results with classical mechanics

Consider a particle trapped in 1D box as shown in fig.

The potential energy of the particle is trapped in 1D box is

V=0 inside the box and

V= outside the box

The steady-state form of Schrodinger’s equation for the particle within the box with above restrictions
may be written as ( V = 0 inside the box )

 2 2m
 E  0...............................(1)
x 2  2

The equation (1) will have the following possible solutions

2mE 2mE
  A sin x...(2)   B cos x......(3)
 

These solutions are subject to the important boundary condition such that =0 for x=0 and x=L

Since cos(0)=1, the second solution cannot describe the particle at x=0 implies B=0

The first solution gives =0 for x=0 but  will be zero at x=L only when

2mE
L  n ....................................(4)

n=1,2,3,…..

From equation (4) , square and rearrange , the energy of the particle can have only certain values called
eigenvalues given by
 n 2 2 2
En  ..............................(5)
2mL2

A particle confined to a box cannot have an arbitrary energy and also n=0 or E=0 is not admissible as
particle is free to move inside the box.

WAVE FUNCTIONS

The wave function of a particle in a box whose energy is E is

2mE
  A sin x...............(6)

Substituting for E from equation (5) we get

2mEn n
 n  A sin x  A sin( ) x.............(7)
 L


 dx  1.............................(8)
2
Further from normalization condition


  
n n
 dx  1    * dx  
2
A sin( ) x * A sin( ) xdx.
  
L L

 

 sin (n / L) x  1  A  [1  cos(2n / L).] / 2dx...........................(9)

2 2 2
A
 

gives

2
A ...............................(10)
L

Therefore the normalized wavefunctions of the particle are

2 n
n  sin x............(11)
L L

The normalized wanefunctions1, 2, 3 are plotted as shown

Graphical explanation

A particle in a box with infinitely high walls is an application of the

Schrodinger equation which yields some insights into particle confinement. The
wavefunction must be zero at the walls and the solution for the wavefunction
yields just sine waves.

The longest wavelength is  = 2L and the higher

modes have wavelengths given by

=2L/n where n= 1,2,3,……….

When this is substituted into the DeBroglie relationship it yields momentum p=h/ =nh/2L

The momentum expression for the particle in a box :

p=h/ =nh/2L: n= 1,2,3,…..

is used to calculate the energy associated with the particle

1 2 p2 n2h2
mv    En ..................(12)
2 2m 8mL2

Same equation as obtained by solving Schrodinger equation.