Matter waves for nonrelativistic particles are described by Schrödinger’s equation,

advanced in 1926 by Austrian physicist Erwin Schrödinger.

--(1)

---------- (2)
𝑑2 𝜓(𝑥) 2𝑚
+ (E-U(x))𝜓(x) = 0 --------------------------- (3)
𝑑𝑥 2 ħ2
𝑑2 𝜓(𝑥)
+ k2 𝜓(x)= 0 ----------------------------------- (4)
𝑑𝑥 2
2𝑚 √2𝑚(𝐸−𝑈)
where, U = potential energy, k2 = (E-U(x) or, k =
ħ2 ħ

The general solution of eqn (4) is

--------------- (5)
in which A and B are constants.
Equation 5 is the time-independent solution of Schrödinger’s equation.
If we wanted to see how the wave function evolves with time, we should multiply
Eq.5 by the time dependence 𝑒 −𝑖𝜔𝑡 :

-------(6)
where first term of right side of eqn (6) represents a wave traveling to the right,
while the second term represents a wave traveling to the left.
1
Free Particle
A Free Particle in Quantum Mechanics is typically described as a particle that is
not under the influence of external or interior potential fields, making its potential
energy virtually zero. In other words, it doesn't experience any forces.
The time-independent Schr𝑜̈ dinger equation for the free particle (1-D) is
ħ2 𝑑2 𝜓(𝑥)
− =E 𝜓(x) ------------------------------- (1)
2𝑚 𝑑𝑥 2
𝑑2 𝜓(𝑥) 2𝑚𝐸
or, + 𝜓(x) = 0
𝑑𝑥 2 ħ2
𝑑2 𝜓(𝑥)
or, +𝑘 2 𝜓(x) = 0 --------------------------- (2)
𝑑𝑥 2
2𝑚𝐸
where, k2 =
ħ2
The general solution to the differential equation (2) is

----------- (3)
Where A and B are constants.
The complete wave function is thus given by the stationary state
𝛙(x, t) = 𝜓(x) 𝑒 −𝑖𝜔𝑡
= (A𝑒 𝑖𝑘𝑥 + B𝑒 −𝑖𝑘𝑥 ) = A𝑒 𝑖(𝑘𝑥−𝜔𝑡) + B𝑒 −𝑖(𝑘𝑥+𝜔𝑡) ---- (4)
Eqn. (4) represents plane simple harmonic wave. The first term on the right side of
equation (4) represents the wave travelling in the positive x-direction, and the
second term represents the wave travelling in the negative x-direction. Therefore,
for the motion of the particle in the positive x-direction, we have
𝛙(x, t) = A𝑒 𝑖(𝑘𝑥−𝜔𝑡)
The square of the wave function of a particle at each point tells us about the
probability of finding the particle around that point.

2
is the probability that the particle will be found at time t at a coordinate in the
range from x to x + dx. The particle is most likely to be found in regions where
|𝜓|2 is large, and so on.
It requires that the wave function be normalized. That is, the integral of
over all possible values of x must equal exactly 1.

The probability distribution function doesn’t depend on position, which says that
we are equally likely to find the particle anywhere along the x-axis!
This also means that the wave function can’t be normalized: The integral of
|𝜓(𝑥, 𝑡|2 overall space would be infinite for any value A.

Probability density neither depends on t and x. This is due to the complete loss of
information about the position and time for a state with definite values of
momentum and energy. According to the Heisenberg’s uncertainty,
when momentum and energy is known exactly, ∇𝑝 = 0, ∇𝐸 = 0, there must be
total uncertainty about its position and time: x -> ∞ and t-> ∞ .
Therefore, in the case of the free particle, the separable solutions do not represent
physically realizable states. A free particle cannot exist in a stationary state.
Sample Question: Show that in the case of the free particle, the separable solutions do not
represent physically realizable states.

3
 𝑑2 𝜓(𝑥)
Problem 1: Show that is a solution of eqn. +𝑘 2 𝜓(x) = 0 .
𝑑𝑥 2

Problem 2: In equation 𝛙(x,t) = A𝑒 𝑖(𝑘𝑥−𝜔𝑡) + B𝑒 −𝑖(𝑘𝑥+𝜔𝑡) keep both terms

A=B=𝜓0 . The equation then describes the superposition of two matter waves of
equal amplitude, traveling in opposite directions.
a) Show that |𝜓(𝑥, 𝑡|2 is then given by

b) Plot this function, and demonstrate that it describes the square of the
amplitude of a standing matter wave.
c) Show that the nodes of this standing wave are located at

and  is the de Broglie wavelength of the particle.

d) Write a similar expression for the most probable locations of the particle.
Soln.
a) The wave function is now given by

b) Consider two plane matter waves traveling in opposite directions along

the x axis. The combined wave  is a standing wave:

4
Thus, the squared amplitude of the matter wave is

5
Particle in a One-Dimensional Box (Infinite square well)
Particle in an Infinitely Deep One-Dimensional Potential Well

Fig. One dimensional box

We consider the one-dimensional motion along x-axis of a particle of mass m in a

hollow rectangular box having perfectly rigid walls.
Let a be the distance between the walls so that the motion along the x- axis is
confined between x= 0 and x= a.
A particle in this potential is completely free, except at the two ends (x = 0 and x
=a), where an infinite force prevents it from escaping.
Outside the well, ψ(x) = 0 (the probability of finding the particle there is zero). Inside
the well, where V = 0, the time-independent Schrödinger equation
d 2 ( x) 2m
+ 2 (E-V)  (x)=0
dx 2

d 2 ( x) 2m
or, + 2 (E-0)  (x)=0
dx 2

6
 d 2 ( x) 2𝑚𝐸
or, + 2  (x)=0
dx 2 ℏ

d 2 ( x)
or, 2
+ k2 (x)=0
dx
2𝑚𝐸
where, k2 =
ℏ2

This is the classical simple harmonic oscillator equation; the general solution is

Where A and B are arbitrary constants. Typically, these constants

are fixed by the boundary conditions of the problem.

ψ(0) = Asin0+ Bcos0 = B,

so B =0, and hence ψ(x) = Asinkx
Then ψ(a) = Asinka, so either A = 0 (in which case we’re left with the trivial—non
normalizable—solution ψ(x) = 0), or else sinka = 0, which means that
ka =0, ±π, ±2π, ±3π, ....
We cannot take A =0, because there will then be no solution. If 0 = A , then the wave
function ψ(x) will be zero everywhere and this is not an acceptable solution. Hence
the equation is satisfied only when
kn = nπ /a , with n =1, 2, 3, ...
We cannot take n = 0, because for n = 0, k =0, E=0 and hence ψ(x) = 0) everywhere
in the box. This means that a particle with zero energy cannot be present in the box.
Hence the wave functions for the motion in the region 0<x<a are given by
𝑛𝜋𝑥
ψn(x) = Asin
𝑎

7
Eigen values of Energy
We have,
2𝑚𝐸 𝑛𝜋
k =√ =
ħ2 𝑎

From this equation we get,

This equation represents the eigen-values of the energy. These values are called the
energy-levels of the particle.
i. the lowest energy of the particle ( n=1),
𝜋 2 ħ2
E1 = , ( it is called the ground state energy-level of the particle.)
2𝑚𝑎2

The values of En in terms of E1, are given by

En =n2 E1
ii. the possible values of energy of the particle in the potential box are
discrete-corresponding to n =1, 2, 3, .........

Normalization of the Wave-Functions

To find A, we normalize ψ:
The total probability that the particle is somewhere in the box must be unity.
Therefore,
𝑎
∫0 | ψn(x)|2 =1

𝑎1 2𝑛𝜋𝑥 𝐴2 𝑎 2𝑛𝜋𝑥
[𝐴2 ∫0 2 [1 − 𝑐𝑜𝑠 ]dx =1 => [𝑥 − 𝑠𝑖𝑛 ]]
𝑎 2 2𝜋𝑛 𝑎

This only determines the magnitude of A, but it is simplest to pick the positive real
root

8
A =√2/a (the phase of A carries no physical significance anyway). Inside the well, then, the
solutions are

The eigenfunctions are therefore

2 𝜋
𝜓1 (𝑥) = √𝑎 sin (𝑎 ) 𝑥 for 𝑛 = 1

2 2𝜋
𝜓2 (𝑥) = √𝑎 sin ( 𝑎 ) 𝑥 for 𝑛 = 2

2 3𝜋
𝜓3 (𝑥) = √𝑎 sin ( 𝑎 ) 𝑥 for 𝑛 = 3

Fig. The first three stationary states of the infinite square well.
As promised, the time-independent Schrödinger equation has delivered an infinite
set of solutions (one for each positive integer n). The first few of these are plotted in
Figure above.
It is evident that wave-function
ψ1 has two nodes at x =0 and x=a.
ψ2 has three nodes at x =0, x= a/2, and x=a.
ψ3 has four nodes at x =0, x= a/3, x= 2a/3 and x=a. ( n+1 nodes)
They look just like the standing waves on a string of length a.

9
[sample question:
A particle of mass m is confined in a field free region between impenetrable walls at x=0 and x=a.
Show that the stationary energy levels of the particle are given by

n2 2 2
En 
2ma 2
Obtain the corresponding wave functions.

OR

10
Solve the Schrodinger wave equation for a particle in one dimensional box and obtain its energy
levels. Show that the eigen-values of energy are discrete.
OR
Determine the energy levels and corresponding normalized wave functions of a particle in one-
dimensional potential well of the form
V(x) = ∞ for x < 0 and for x > a
= 0 for 0<x<a

Mathematical Problem
1. Find the lowest energy level of an electron confined to move in a one-
dimensional potential box of length 1Å. (ħ=1.05× 10−34 Js)

Soln.:
We have,
12 𝜋2 ħ2
a = 1Å = 10-10 m, E1 = = 6× 10−18 J = 600/16 = 37.5 eV.
2𝑚𝑎2

2. Find the lowest energy of neutron confined to a nucleus of size 10-14 m.

(mn= 1.67× 10−27 kg)

Soln.
12 𝜋2 ħ2
a = 10 -14 m, E1 = = 3.28× 10−13 J = (32.8/16)× 106 eV=2.05 MeV
2𝑚𝑎2

. 3. The normalized wave function of a particle in one-dimensional box of width a

2 𝑛𝜋
is 𝜓𝑛 (𝑥) = √𝑎 sin ( 𝑎 ) 𝑥, determine the value of <x> and <x2>

Soln.

<x> = ∫ 𝜓𝑛∗ (𝑥) x 𝜓𝑛 (x)dx

𝑎 2 𝑛𝜋 2 𝑛𝜋
= ∫0 √ sin ( ) 𝑥 x √𝑎 sin ( 𝑎 ) 𝑥 dx
𝑎 𝑎

11
 2 1 𝑎 2𝑛𝜋𝑥
= . ∫ 𝑥 [cos 0 − 𝑐𝑜𝑠 ] 𝑑𝑥
𝑎 2 0 𝑎
1 𝑎 1 𝑎 2𝜋𝑛𝑥 𝑑𝑢
= 𝑎 ∫0 𝑥𝑑𝑥 - ∫ 𝑥𝑐𝑜𝑠 dx ∫ 𝑢𝑣𝑑𝑥 = 𝑢 ∫ 𝑣 𝑑𝑥-∫ {𝑑𝑥 ∫ 𝑣𝑑𝑥}dx
𝑎 0 𝑎

1 𝑎2 1 𝑎 2𝜋𝑛𝑥 𝑎 𝑎 𝑎 2𝜋𝑛𝑥
= 𝑎. - [𝑥. 2𝜋𝑛 . 𝑠𝑖𝑛 |0 − ∫0 {2𝜋𝑛 . 𝑠𝑖𝑛 } 𝑑𝑥]
2 𝑎 𝑎 𝑎

𝑎 1 𝑎 𝑎 2𝜋𝑛𝑥 𝑎
= 2 - 𝑎 [0 + 2𝜋𝑛 . 2𝜋𝑛 𝑐𝑜𝑠 |0 ]
𝑎
𝑎 1
= 2 - 4(𝜋𝑛)2 (1-1)
𝑎
=2

2 𝑎2 𝑎2
<x2> do yourself [Ans. 𝑎( 6 - 4(𝑛𝜋)2 )

Example 4: An important property of the eigenfunctions of a system is that they are orthogonal to
one another, which means that
∞
∫−∞ 𝜓𝑚 𝜓𝑛 𝑑𝑥 = 0, 𝑚≠𝑛
Verify this relationship for the eigenfunctions of a particle in a one-dimensional box.

Solution: Let 𝑚 = 1 and 𝑛 = 2.

For a particle in a one-dimensional box
2 𝜋
𝜓1 (𝑥) = √𝑎 sin (𝑎 ) 𝑥

2 2𝜋
𝜓2 (𝑥) = √𝑎 sin ( 𝑎 ) 𝑥.

∞ ∞ 2 𝜋 2 2𝜋
Now ∫−∞ 𝜓1 𝜓2 𝑑𝑥 = ∫−∞ (√𝑎 sin (𝑎 ) 𝑥 √𝑎 sin ( 𝑎 ) 𝑥) 𝑑𝑥

2 ∞ 1 𝜋 3𝜋
= 𝑎 ∫−∞ 2 [cos (𝑎 ) 𝑥 − cos ( 𝑎 ) 𝑥] 𝑑𝑥
𝜋 3𝜋 ∞
1 sin(𝑎)𝑥 sin(
𝑎
)𝑥
= [ 𝜋 − 3𝜋 ]
𝑎
𝑎 𝑎 −∞

= [𝜋(∞ + ∞) − 3𝜋(∞ + ∞)]

= 0.
H.W.

12
 2 𝑛𝜋
Show that the wave functions 𝜓𝑛 (𝑥) = √𝑎 sin ( 𝑎 ) 𝑥 and 𝜓𝑚 (𝑥) =

2 𝑚𝜋
√ sin ( )𝑥 are orthogonal.
𝑎 𝑎

Finite Potential Well

Figure shows a potential well given by
𝑉(𝑥) = 0, 0 < 𝑥 < 𝐿
(1)
= 𝑉0 , 𝑥 < 0 and 𝑥 > 𝐿 .

Fig. 1: A square potential well with finite barriers. The energy E of the trapped particle is less than the
height U of the barriers.

The well contains a particle whose energy E is less than 𝑉0 . According to classical
mechanics when the particle strikes the sides of the well, it bounces off without
entering regions I and III. In quantum mechanics, the particle also bounces back and
forth, but now it has a certain probability of penetrating into regions I and III even
though 𝐸 < 𝑉0 .
In regions I and III Schrödinger’s steady-state equation is
𝑑 2 𝜓(𝑥) 2𝑚
+ [𝐸 − 𝑉0 ]𝜓(𝑥) = 0, 𝑥 < 0 and 𝑥 > 𝐿
𝑑𝑥 2 ℏ2
𝑑 2 𝜓(𝑥)
or − 𝛼 2 𝜓(𝑥) = 0., (2)
𝑑𝑥 2

√2𝑚(𝑉0 −𝐸)
where 𝛼= . (3)
ℏ

Solutions of Eq. (2) are

13
 𝜓I = 𝐶𝑒 𝛼𝑥 + 𝐷𝑒 −𝛼𝑥 , 𝑥 < 0 (4)
𝜓III = 𝐹𝑒 𝛼𝑥 + 𝐺𝑒 −𝛼𝑥 , 𝑥 > 𝐿. (5)
Both 𝜓I and 𝜓III must be finite everywhere. Since in region I, 𝑒 −𝛼𝑥 → ∞ as 𝑥 →
−∞ and in region III, 𝑒 𝛼𝑥 → ∞ as 𝑥 → ∞, the coefficients D and F must therefore
be 0. Hence we have
𝜓I = 𝐶𝑒 𝛼𝑥 , 𝑥 < 0 (6)
𝜓III = 𝐺𝑒 −𝛼𝑥 , 𝑥 > 𝐿 . (7)
Within the well (region II), 𝑉(𝑥) = 0, and the Schrödinger equation is
𝑑 2 𝜓(𝑥)
+ 𝑘 2 𝜓(𝑥) = 0, 0 < 𝑥 < 𝐿, (8)
𝑑𝑥 2

√2𝑚𝐸
where 𝑘= . (9)
ℏ

The solution of Eq. (8) is

√2𝑚𝐸 √2𝑚𝐸
𝜓II = 𝐴sin𝑘𝑥 + 𝐵cos𝑘𝑥 = 𝐴sin 𝑥 + 𝐵cos 𝑥. (10)
ℏ ℏ

In the case of a well with infinitely high barriers, we found that 𝐵 = 0 in order that
𝜓 = 0 at 𝑥 = 0 and 𝑥 = 𝐿. However, in this case, 𝜓𝐼𝐼 = 𝐶 at 𝑥 = 0 and 𝜓𝐼𝐼 = 𝐺 at
𝑥 = 𝐿, so both the sine and cosine solutions of Eq. (10) are possible.
Our calculations so far show that the bound-state wave functions for a finite well are
sinusoidal inside the well [Eq. (10)] and exponential outside it [Eq. (6, 7)]. We have
to match the wave functions inside and outside the well so that they satisfy the
boundary conditions: 𝜓(x) and d𝜓(x)/dx must be continuous at the boundary points
at x= 0 and x= L.
Matching the sinusoidal and exponential functions at the boundary points so that
they join smoothly is possible only for certain specific values of the total energy so
this requirement determines the possible energy levels of the finite square well.

14
It can be shown that the transmission probability is
√8𝑚(𝑉0 −𝐸) 𝐿
𝑇 = 𝑒 −2𝛼𝐿 = 𝑒 − ℏ . (11)
This tunneling effect is useful to explain the alpha decay.
Example: Show that the equation 𝜓(𝑥) = 𝐶𝑒 𝛼𝑥 + 𝐷𝑒 −𝛼𝑥 is a solution of the time independent
Sch𝑜̈ rdinger equation outside of a finite well of height V0 .
Soln.
We know the Sch𝑜̈ rdinger equation outside of a finite well of height V0 is

𝑑2 𝜓(𝑥) 2𝑚
+ 2 [𝐸 − 𝑉0 ]𝜓(𝑥) = 0
𝑑𝑥 2 ℏ

𝑑2 𝜓(𝑥)
or, − 𝛼 2 𝜓(𝑥 ) = 0.
𝑑𝑥 2
𝑑2 𝜓(𝑥)
or, = 𝛼 2 𝜓(𝑥 )
𝑑𝑥 2
We have to show that the given eqn satisfies the above eqn.

15
 𝑑𝜓(𝑥) 𝑑
Now, = (𝐶𝑒 𝛼𝑥 + 𝐷𝑒 −𝛼𝑥 ) =C𝛼𝑒 𝛼𝑥 - 𝛼D𝑒 −𝛼𝑥
𝑑𝑥 𝑑𝑥

𝑑2 𝜓(𝑥)
or, = C𝛼 2 𝑒 𝛼𝑥 + 𝐷 𝛼 2 𝑒 −𝛼𝑥 = 𝛼 2 (C𝑒 𝛼𝑥 +D𝑒 −𝛼𝑥 ) =𝛼 2 𝜓(𝑥)
𝑑𝑥 2

Problem 2: Electrons with energies of 1.0 eV and 2.0 eV are incident on a barrier 10.0 eV high
and 0.50 nm wide. (a) Find their respective transmission probabilities. (b) How are these affected
if the barrier is doubled in width?

Soln.

a) For the 10 eV electrons

√2𝑚(𝑉0 − 𝐸)
𝛼=
ℏ
√(2)(9.1×10−31 𝑘𝑔)[(10−1)𝑒𝑉](1.6×10−19 𝐽/𝑒𝑉
=
1.054×10−34 𝐽𝑠
= 1.6× 1010 𝑚 −1

Since L = 0.50 nm = 5× 10−10 m,

2𝛼𝐿= (2) (1.6× 1010 𝑚−1 )( 5× 10−10 m) =16
The approximate transmission probability is
T1 =𝑒 −2𝛼𝐿 = 𝑒 −16 = 1.1× 10−7

For the 2 eV electron a similar calculation gives, T2 =2.4× 10−7

These electrons are over twice as likely to tunnel through the barrier.

b) If barrier is doubled in width to 1 nm, the transmission probabilities become

𝑇1′ = 1.3× 10−14 and 𝑇2′ =5.1× 10−14

Evidently T is more sensitive to the width of the barrier than to the particle energy here.

Tunneling
In quantum mechanics a particle can penetrate into a barrier where it would be
classically forbidden.

16
A finite-height square barrier is described by the following potential-energy
function:
0 𝑥<0
U(x) = {𝑈0 0<𝑥<𝐿 ---------------------- (1)
0 𝑥>𝐿

Suppose a uniform and time-independent beam of electrons or other quantum

particles with energy E traveling along the x-axis (in the positive direction to the
right) encounters a potential barrier described by the above Equation.

The time-independent Schrӧdinger equation for a particle in the beam.

The general form of this equation is given by Equation 2, which we
reproduce here:

------------ (2)

We divide the real axis into three regions with the boundaries defined by the
potential function in Equation 1

17
The continuity condition at region boundaries requires that:

We can easily verify that in regions I and III, the solutions must be in the
following general forms:

---------- (2)

The constants A, B, F, and G in Equations may be complex.

18
In region I, there are two waves—one is incident (moving to the right) and one is
reflected (moving to the left)—so none of the constants A and B in Equation 1st
may vanish. In region III, there is only one wave (moving to the right), which is the
transmitted wave, so the constant G must be zero in Equation 2nd, G=0. We can
write explicitly that the incident wave is ψin(x)=Ae+ikx and that the reflected wave is
ψref(x)=Be−ikx, and that the transmitted wave is ψtra(x)=Fe+ikx.
In region II, the eqn is

--------------------- (3)

The general solution to Equation 3 is not oscillatory (unlike in the other regions) and
is in the form of exponentials that describe a gradual attenuation of ψII(x),

The two types of solutions in the three regions are illustrated in Figure

19
Now we use the boundary conditions to find equations for the unknown constants.
Equations
A+B=C+D.
and

similarly,

and

Solving these equations

In deriving Equation, to avoid the clutter, we use the substitutions γ≡β/k−k/β, and
the definition of hyperbolic functions:

20
Linear Harmonic Oscillator
Oscillations are found throughout nature, in such things as electromagnetic waves,
vibrating molecules, and the gentle back-and-forth sway of a tree branch.
A simple harmonic oscillator is a particle or system that undergoes harmonic motion
about an equilibrium position, such as an object with mass vibrating on a spring.
In this section, we consider oscillations in one-dimension only. Suppose a mass
moves back-and-forth along the x-direction about the equilibrium position, x = 0.
We cannot use this formulation to describe vibrations of diatomic molecules, where
quantum effects are important.
The time-independent Schrödinger wave equation for linear motion of a particle along
the x-axis is
𝑑 2 𝜓(𝑥) 2𝑚
+ [𝐸 − 𝑉 ]𝜓(𝑥) = 0. ----------------------- (1)
𝑑𝑥 2 ℏ2

For a linear harmonic oscillator, the potential energy is

21
 1
𝑉(𝑥) = 𝑘𝑥 2 , (1)
2

where k is the restoring force parameter.

Fig.1: The potential energy of a linear harmonic oscillator.

𝑘
ω=√ => k = m𝜔2
𝑚

------------------------ (2)
Substituting the value of V in equation (1) we get,

𝑑 2 𝜓(𝑥) 2𝑚 1
+ [𝐸 − 𝑚𝜔2 𝑥 2 ] 𝜓(𝑥) = 0.
𝑑𝑥 2 ℏ2 2
𝑑 2 𝜓(𝑥) 2𝑚𝐸 𝑚𝜔2 𝑥 2
or, +⌊ − ⌋ 𝜓(𝑥) = 0 ------------------------------ (3)
𝑑𝑥 2 ℏ2 ℏ2

This is the Schrodinger wave equation for the oscillator

Simplification of the wave equation for the harmonic oscillator:
To simplify the equation (3) we introduce a dimensionless independent
variable “y” which is related to “x ” by the equation

or, -------------- (4)

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Where,

Now we have
d d dy d
  
dx dy dx dy

-------- (5)
substituting these values in equation (3), we get

----- (6)
Dividing through by  2

or,

------------ (7)

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 ----- (8)
Eigen values of the total energy En for the harmonic oscillator
The solutions to the eqn(8) that are acceptable here are limited by the condition that
   0 as y    in order that

 2


 dy  1 , otherwise the wave function cannot represent an actual
particle. The mathematical properties of eq. (8) are such that this condition will be
fulfilled only when
  2n  1 , n= 0, 1, 2, 3, ...............

The energy of a harmonic oscillator is thus quantized in steps of ℎ𝜈. We note that
when 𝑛 = 0,
1
𝐸0 = ℎ𝜈
2
which is the lowest value the energy of the oscillator can have. This value is called
the zero-point energy because a harmonic oscillator in equilibrium with its

24
surroundings would approach an energy of 𝐸 = 𝐸0 and not 𝐸 = 0 as the temperature
approaches 0K.

Problem:
The potential energy of a SHO of mass m, oscillating with angular frequency  is

a) Write the time-independent SchrÖdinger equation for a simple harmonic

oscillator.

b) Given the eigen-function of the Hamiltonian operator for the ground state is
1
  4 m
 0    e x /2 , where  
2
, calculate the energy eigen value in the
 
ground state.
Solution:
a) The Hamiltonian operator for the oscillator is
2
d2 1 2 2
Hˆ     x
2m dx 2 2

Therefore, the time-independent SchrÖdinger equation is

 2 d2 1 
 2
 m 2 x 2  ( x)  E ( x)
 2m dx 2 

b) For the ground state the SchrÖdinger equation is

 2 d2 1 
 2
 m 2 x 2  0  E 0 ------------------ (1)
 2m dx 2 
Now,
1
  4
 0    e x /2
2

 

25
 1
x
d   4 
2

 0    e 2 ( x)   x 0 ----------- (2)

dx   

and
d 2 0 d
2
  x 0   0   x( x 0 )   0   2 x 2 0   0
dx dx

d 2 0
 2   2 x 2 0   0 -------------------------- (3)
dx
2
Multiplying the eqn.(3) by 
2m

d 2 0
2 2
 2
  2 x 2 0   0
2m dx 2m 2m
m
Substituting   and simplifying we get

 2 d2 1 2 2 1
 2
 m x  0   0 --------------------- (4)
 2m dx 2  2

Comparing eqns. (1) and (4)

1
E0  
2

Problem:
The vibrational frequency of the hydrogen iodide HI diatomic molecule is
6.69×1013 Hz

a. What is the force constant of the molecular bond between the hydrogen and
the iodine atoms?
b. What is the energy of the emitted photon when this molecule makes a
transition between adjacent vibrational energy levels?

Soln.

a)

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 = (1.67× 10-27 kg ) (2𝜋 × 6.69 ×1013 Hz)2 = 295N/m

b)

= (4.14×10-15 eV.s) (6.69 ×1013 Hz) = 0.277eV

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