Application of Schrodinger Wave Equations:

Particle in a One Dimensional Deep Potential Well (box)

Let us consider a particle of mass ‘m’ in a deep well restricted to move in a one dimension (say x). Let us
assume that the particle is free inside the well except during collision with walls from which it rebounds
elastically.

The potential function is expressed as

……………………….(1)

The probability of finding the particle outside the well is zero (i.e.ψ=0). Inside the well, the Schrödinger’s
time independent wave equation is written as

For free particle, i.e. V=0

Let

Then equation (3) becomes

and writing the Schrodinger’s wave equation for 1-D

The general equation of above equation may be expressed as

)
Where A and B are constants to be determined by boundary conditions
Condition I:
At x = 0, potential energy V=∞. Therefore, there is no chance for finding the particle at wall of the box

Therefore from equation (6)

 equation (6) can be written as

Condition II:
At x = L, potential energy V=∞. Therefore, there is no chance for finding the particle at wall of the box

Therefore from equation (7) becomes

Here either A=0 or sin kL=0; but A≠0 because if A=0 , the entire function will be zero as B=0
Therefore then
where n = 1,2,3,4

Now from equation (7) wave function becomes

)

Substituting the value of k from (8) in (4), we get

( )

This gives

or

,…. ……..(10)
Where n = 1,2,3,4……
From equation (10) En is the energy value (Eigen Value) of the particle in a well. It is clear that the energy
values of the particle in box (well) are discrete not continuous i.e. the energy of the particle is quantized.
The discrete energy values are given by

Similarly we can get the other energy values

In general we can write the energy Eigen value as

Fig: Energy for Particle
It is found that from the energy levels E1,E2,E3 etc the energy levels of an electron are discrete.
This is the great success which is achieved in Quantum Mechanics than classical mechanics, in which the
energy levels are found to be continuous.
Eigen Function (Normalized Wave Function):
It is the process by which the probability (P) of finding the particle (electron) inside the box can be done.
We know that condition of normalization of wave function, the total probability (P) is equal to 1 means then
there is a particle inside the box.
For a one dimensional potential box of length ’L’ the probability
Equation of wave function is

The probability density

| |

The probability density is zero at x = 0 and x = L. since the particle is always within the well

∫ | |

∫ ( )

∫ ( )

∫ ∫
 √

Substituting A in equation (12), we get

The above equation (14) is normalized wave function (Eigen function) belonging to energy value En and
gives the wave function of the particle enclosed in infinitely deep potential well.
The normalized wave function ψ1, ψ2 and ψ3 together with the probability densities | | | | and| |

Physical interpretation of wave function:

Let us consider the first three cases:
Case I: For n=1 (Ground State): This is known as ground state and the particle is normally found in this
state

The Eigen function in this case is given by

At x=0 and x=L, the value of ψ1=0.

ψ1 has maximum for x = L/2

The probability is zero at x = 0 and x = L and maximum at x = L/2. Therefore in ground state, the particle
can not found at the walls of the box and the probability of finding is maximum at central region.
Case II: For n =2 (First Excited state)
In this case
The Eigen function of this case is given by

For values of x = (0, L/2, and L), ψ2 =0. Further ψ2 has maximum value for x = L/4 and x = 3L/4

From above observation, the particle can not be observed either at walls nor at the center. The maximum
probability of finding the particle is either at x = L/4 or 3L/4.
Case III: (Second Excited State):
The energy in this state is given by

The Eigen wave function is given by

Here ψ3 = 0 for x= 0, L/3, 2L/3 and L

It is observed that the particle is most likely found at location x = L/6, L/3 and 5L/6

Particle in three dimensional Potential box:

Let us consider that a particle is trapped in a 3-D rectangular box of sides a, b, and c parallel to x, y and z
axis respectively.
The particle can move freely within the region 0 < x < a, 0 < y < b, 0 < z < c. Because the potential inside
the box is zero, so there is no force on the particle inside the box. Thus the potential energy can be defined
as

{ }

{ }

Since the particle cannot penetrate the walls of box due to infinite potential, it cannot exist outside the box.
i.e.

{ }

For this free particle, Schrodinger’s time independent equation (3- D time independent) is

⃗⃗⃗ ⃗⃗⃗

⃗⃗⃗ ⃗⃗⃗ ⃗⃗⃗

⃗⃗⃗

To solve this equation we use method of separation of variables. Let us consider

⃗⃗⃗

Where X(x), Y(y) and Z(z) are functions of only x, y, and z respectively. Putting the value of ⃗⃗⃗ in equation

(4)

[ ] [ ] [ ] [ ]

Or

[ ]

Dividing above equation by

Since all three term on LHS are independent to each other so we can take them equal to some constant
individually.
For this, let us consider

{ }
And then from equation (5) , we get

The general Solution of equation

Condition 1: Applying boundary condition at x = 0 potential energy V=∞. Therefore, there is no chance for
finding the particle at wall of the box.
i.e. X(x) = 0

Then from equation (8), we get

Putting the value of B in equation (8), we get

Condition 2: At x = a, potential energy V=∞. Therefore, there is no chance for finding the particle at wall of
the box i.e. X(x) = 0

From equation (9), we get

Here either A=0 or sin kxa=0; but A≠0 because if A=0 , the entire function will be zero as B=0
Therefore A≠0 then

Similarly Along Y and Z axis

Putting the value of in equation (9), we have

Similarly along Y and Z axis

Putting the value of kx, ky and kz in equation (7), we get

Eigen value of particle

[ ]

Where
Eigen Function:
It is the process by which the probability (P) of finding the particle (electron) inside the box can be done.
We know that condition of normalization of wave function, the total probability (P) is equal to 1 means then
there is a particle inside the box.
Normalized condition

∫ | |

Putting the value of ‘A’ in equation (10a)

Similarly along y and z directions

√
With
So, the normalized wave function corresponding to wave associate with the particle moving in 3-D box is
⃗⃗⃗ )

⃗⃗⃗ √ ( ) ( ) ( )

And from equation (10), Eigen values of energy for the particle is

[ ]

[ ]

Where

Eigen value of particle

[ ]

[ ]

And Eigen function

⃗⃗⃗ √
( ) ( ) ( )
√
Concept of degeneracy:
Degenerate state:
When there is only one wave function corresponding to one particular energy Eigen value, the level is
known as non-degenerate state. But when there is a number of wave function corresponding to a single
energy Eigen value, then the level is known as degenerate. If there are g such levels which correspond to the
same energy then state is known a g- fold degenerate state.

For nx = ny = nz =1, [ ] the energy corresponds to single Eigen

function, the same is true for nx = ny = nz =2 and nx = ny = nz =3 etc. such Eigen states are non-degenerate
states.

For nx = 1, ny = 1 nz =2; nx =1, ny =2, nz =1; nx = 2, ny =1, nz =1 the energy Eigen values is

[ ]

corresponds to three Eigen function Ψ112, Ψ121 and Ψ211. Such states are known as degenerate

state. This state is 3- fold degenerate sate or the order of degeneracy is 3.

Energy Levels and order of degeneracy
Energy Possible combination of Order of degeneracy

(1,1,1) 1 (non- degenerate state)

(1,1,2),(1,2,1),(2,1,1) Order of degeneracy = 3

(1,2,2), (2,1,2),(2,2,1) Order of degeneracy = 3

(2,2,2) 1 (non- degenerate state)

(1,1,3), (1,3,1),(3,1,1) Order of degeneracy = 3

(1,2,3),(2,3,1),(3,1,2)
Order of degeneracy = 6
(3,2,1),(1,3,2),(2,1,3)