2-Energy and Wave Function of A Particle in Two and Three Dimensional Box-16-Aug-2023
2-Energy and Wave Function of A Particle in Two and Three Dimensional Box-16-Aug-2023
2-Energy and Wave Function of A Particle in Two and Three Dimensional Box-16-Aug-2023
Module: 1
Numerical on de Broglie’s hypothesis
𝒉 𝒉 𝒉 𝒉
𝝀= = = =
√
𝒑 √ 𝟐 𝒎( 𝑲 . 𝑬 ) 𝟑 √ 𝟑 𝒎𝒌𝑻
𝟐𝒎 𝒌𝑻
𝟐
WAVE FUNCTION
&
SCHRODINGER'S WAVE EQUATION
WAVE FUNCTION
A variable quantity which characterizes de Broglie waves is known as wave function.
The wave function is represented by the symbol
The value of the wave function associated with a moving particle at point (x, y, z) and time
‘t’ gives the probability of finding the particle at that time and at that point.
WAVE FUNCTION
PHYSICAL SIGNIFICANCE OF WAVE FUNCTION
The wave function has no physical meaning.
ψ×ψ*= │ψ │2 is real and positive, amplitude may be positive or negative, but the intensity(square of
amplitude) is always real and positive.
ψ×ψ*=│ ψ │2 represents the probability density or probability of finding the particle in the given
region.
The probability density P (x, t), product of the wave function ψ and its complex conjugate
ψ*, is a measure of probability density i.e., probability per unit volume of the particle being at a
point.
2 2
P( x , t ) ( x , t )
Properties of wave function
The wave function ψ should satisfy the following properties to describe the characteristics of matter
waves.
1. ψ must be a solution of Schrödinger wave equation.
a b
2. The wave function ψ should be continuous and
single valued everywhere (x)
(x)
3. Ψ is finite everywhere
P x
4 The first derivative of ψ with respect to x should be P x
continuous and single valued everywhere, since it is
related to the momentum of the particle which should
be finite.
c
5. Ψ must be normalized so that ψ must go to 0 as x → d
(x) (x)
± , so that ∫ d over all the space be a finite
2
constant.
R x Q x
Figure b, c, and d do not represent wave functions
SCHRODINGER'S WAVE EQUATION
If |ψ|2 d is the probability of finding the particle in a small volume dτ then total probability of finding a particle
anywhere inside volume τ must be 1 i.e.,
d 1
2
Note: When the particle is bound to a limited region the probability of finding the particle
at infinity is zero i.e.,
0 at x
*
Schrödinger time- independent one-dimensional wave equation
8 m
2 2
2 ( E V ) 0
x 2
h
Here ψ is a function of x alone and is independent of time
2 2
𝜕 𝜓 8𝜋 𝑚
2
+ 2
(𝐸 −𝑉 )𝜓=0
𝜕𝑦 h
2
2 8 𝜋 𝑚
𝛻 𝜓 ( 𝑟 ) + 2 (𝐸 − 𝑉 )𝜓(𝑟)=0
h
=+
Eigen functions and Eigen values
The physically acceptable solutions of SWE are called Eigen functions (ψ).
The physically acceptable wave functions ψ must satisfy the following conditions:
1. ψ is single valued.
2. ψ and its first derivative with respect to its variable are continuous everywhere.
3. ψ is finite everywhere
Eigen values: The eigen functions are used in Schrö dinger wave equation to evaluate the
physically measurable quantities like energy, momentum, etc., these values are called Eigen
values.
Example : In an operator equation
where is an operator for the physical quantity and is an Eigen function and λ is the Eigen value.
Example2: Energy
Operator H E
H → total energy (Hamiltonian) operator, ψ → Eigen function and E → total energy in the system.
Example3:
Momentum P p
Operator
P → momentum operator and p → momentum eigen values.
Applications of Schrodinger’s wave equation(1-D box) 2 8 2 m
2 ( E V ) 0
1. Particle in an one-dimensional potential well of infinite depth (Particle in a box) x 2
h
Let us start with a particle of mass ‘m’ moving freely in x- direction in the region from
x=0 to x=a.
The potential energy V(x) = for x<0 and x>a
Region I Region II Region II
V(x) = 0 for 0 ≤ x ≤ a
Outside the box Schrodinger’s wave 2 8 2 m
equation is
2 E 0............(1)
x 2
h
particle cannot be found at all V= V=0 V=
Where =0 for all points outside the box i.e., 2 0
outside the box
2
k 2
0..............( 2)
x 2
8m 2 E
where k
2
............(3)
h2
The solution of equation (2) is A cos kx B sin kx..........(4)
where A & B are constants which depends on the boundary conditions of the well.
applying boundary conditions
Condition: I at x =0, = 0.
Substituting the condition, I in SWE solution, we get A =0 and B0
(If both A and B = zero for all values of x, then ψ is zero. Which means the particle is not present in the well)
a
8m 2 E
Now we have k
2
h2
n 22
k 2
2
On equating and n 2h 2
simplifying we get E 2
................(6)
8ma
The above equation gives the energy values or Eigen values of the particle in the well.
When n=0, n = 0. This means to say that the particle is not present inside the box, which violates our initial
assumption. Hence n0 and the lowest value of ‘n’ is 1.
The lowest energy corresponds to ‘n’=1 is called the zero-point energy or Ground state energy.
h2
E zero po int
8ma 2
B2 a B2a 2
a
2 n sin 2 n 0 1 1 B
2 2 a
Thus the normalized wave function of a particle in a one-dimensional box is given by,
2 n
n sin x where, n=1,2,3……………
a a
This equation gives the Eigen functions of the particle in the box. The Eigen
functions for n=1,2,3.. are as follows.
2
1 sin x
a a
2 2
2 sin x
a a
2 3
3 sin x
a a
Eigen functions and Eigen values
Case (1): n=1.
Ground state and the particle is normally found in this state.
2
For n=1, the Eigen function is 1
2
1 sin x x=0 x=a/2 x=a
1 =0 at x=0 & x=a a a
1 has a maximum value for x=a/2.
2 a 2
1 sin
a a2 a 1
At ground state the particle cannot be found at the walls of the box and the probability of finding the particle is
maximum at the central region.
In the first excited state the particle cannot be observed either at the walls or at the center
|3|2=0 for the values x=0, a/3, 2a/3, a and |3|2 reaches maximum 2/a at x=a/6,
a/2, 5a/6 at which the particle is most likely to be found.
.
The energy corresponding to second excited state → E3=9E1
Applications of Schrodinger’s wave equation contd…
2. Free Particle:
A particle, which is not under the influence of any kind of field or force.
Thus, it has zero potential, i.e., V=0 over the entire space.
2 8 2 m
2 E 0
x 2
h
h 2
2 2 E
8 m x
The above equation holds good for a particle for which the potential V=0 over the entire
space
Let us extend the case of particle in an infinite potential well to the free particle case, by treating
the width of the well to be infinity, i.e., by allowing a =
n 2h 2
E where n = 1, 2, 3…
8ma 2
Particle in a 3-D box :
2 2 2
(𝑛¿ ¿ 1 + 𝑛 +𝑛 )h 2
2 3
𝐸𝑛 𝑛 𝑛 = ¿
1 2 3
8 𝑚𝑎2
E0
Where n1 = 1, 2, 3, ………..
n2 = 1, 2, 3, ………..
n3 = 1, 2, 3, ………..
(12+12+12)E0 = 3E0
3
= (12+22+12)E0 = 6E0
= (22+12+22)E0 = 9E0