Lecture notes on Quantum Mechanics

1 Introduction
Classical (Newtonian) mechanics has been successful in explaining the motion of
objects which are directly observable (i.e. macroscopic) but it fails to explain the
motion of particles which belong to microscopic scale. It cannot explain the stability
of the atom, spectrum of Hydrogen atom, black body spectrum etc.
A body that absorbs the entire radiation incident on it, is called a perfect (ideal)
blackbody. When this perfect blackbody is heated, it emits radiation at all frequen-
cies and hence is a good radiator and absorber. As shown in Figure, experimental
results show that at a given temperature, the radiation energy density initially in-
creases with increasing wavelength, then peaks at a particular wavelength λm , and
after that decreases at higher wavelengths.
Classical mechanics fails to ex-
plain this profile at shorter wave-
lengths/higher frequencies. In 1900
Max Planck could successfully explain
the blackbody profile, by stating that an
oscillating atom can absorb or radiate
energy only in multiples of hν, where
each discrete unit is called as an energy
quantum. h is called as the Planck con-
stant. Einstein extended Planck hypoth- Figure 1: Blackbody radiation spectrum
esis and proved the particle nature of
light with his successful explanation of the photoelectric effect. de Broglie intro-
duced the concept of matter waves and suggested that light has a dual nature con-
sisting of waves and particles.

The wave-particle duality and the concept of quantization, resulted into the devel-
opment of the field of quantum mechanics.

2 Heisenberg Uncertainty Principle

Classical mechanics says that at any instant of time the state of a particle can be
specified by its position and momentum. This implies that at any time the state of
a particle can be known with reference to its initial state.

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 Heisenberg showed that it is not possible to have an ‘exact’ measurement of
the position and time of a particle. If ∆x is the uncertainty for position in the
x-coordinate and ∆p is the uncertainty in momentum, then

~
∆x · ∆p ≥
2
(1)

~ ~
Similarly, ∆E · ∆t ≥ and ∆J · ∆θ ≥
2 2

3 Wave function
Micro-particles exhibit wave properties and hence the de Broglie wave for the same
can be represented by a complex-valued wave function Ψ, which describes the wave
as a function of position and time.

Probability (P) of finding the particle in an infinitesimal volume dV (= dx × dy

× dz) is proportional to |Ψ(x, y, z)|2 dx dy dz at time t;
i.e. P ∝ |Ψ(x, y, z)|2 dV.
|Ψ|2 is called the probability density and Ψ is the probability amplitude.

Ψ is a complex function. For the probability to be a real value,

Z +∞
ΨΨ∗ dV = 1
−∞
(2)

where Ψ∗ is the complex conjugate of Ψ.

3.1 Properties of the wave function

1. Ψ should be finite for all values of x,y,z.

2. Ψ should be single-valued.

3. Ψ should be continuous across any boundary.

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4 Schrödinger wave equation
Erwin Schrödinger developed a wave equation to describe the behaviour of matter
waves; which will define the wave properties of electrons and also predicts the
particle behaviour.
The wave function for a de Broglie wave with angular frequency ω travelling in
+x direction is given as

Ψ = Aei(kx−ωt)
(3)

which can be written as

Ψ = ψe−iωt
(4)

where ψ = Aeikx .
Differentiating the above twice w.r.t x, we get

d2 Ψ 2
−iωt d ψ
= e (5)
dx2 dx2
Differentiating w.r.t t, we get

d2 Ψ
= −ω 2 e−iωt ψ (6)
dt2
A travelling wave with displacement y, and velocity v can be represented by

d2 y 1 d2 y
= (7)
dx2 v 2 dt2
In analogy with the above, the de Broglie wave for the motion of a free particle
can be given by,

d2 Ψ 1 d2 Ψ
= (8)
dx2 v 2 dt2
Substituting equations 5 and 6 into the above equation 8, we obtain

d2 Ψ 1
e−iωt 2
= 2 (−ω 2 e−ωt Ψ)
dx v
(9)

d2 Ψ ω2
= − 2Ψ (10)
dx2 v

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 For a wave with frequency ν and wavelength λ, we have
ω = 2πν and v = νλ. Then equation 10 can be written as,

d2 Ψ 4π 2
= − Ψ (11)
dx2 λ2
Hence,

1 1 d2 Ψ
= − (12)
λ2 4π 2 Ψ dx2
For a particle of mass m and moving with a velocity v, we have its K.E. =
1/2mv 2 = p2 /2m.

1 h2
Since p = h/λ, we get K. E. = .
2m λ2

Also, total energy of the particle, E = K.E. + P.E. = K.E. + V , where V (x)

Substituting equation 12 and that for K.E., into the expression for total energy,
we get

h2 1 d2 Ψ
E=- +V (13)
8π 2 m Ψ dx2
Hence,

d2 Ψ 8π 2 m
= − (E − V )Ψ (14)
dx2 h2
The above can be also written as
d2 Ψ 8π 2 m
+ (E − V )Ψ = 0 (15)
dx2 h2
Equation 15 is the time independent Schrödinger equation. It can be also written
as
d2 Ψ 2m
+ 2 (E − V )Ψ = 0 (16)
dx2 ~
The Schrödinger equation can be solved to obtain the wave function, for a
known potential energy, initial and boundary conditions of the physical system.

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 For bound particles, the solution of wave function of the Schrödinger’s equations,
will be satisfied only for specific values of energy. These energy values are discrete and
are called eigen values of the energy of the particle. The solutions of the corresponding
wave functions are called eigen functions.

German origin : eigen values ⇒ eigenwart ⇒ proper or characteristic value. Eigen-

funktion ⇒ proper or characteristic function.

5 Infinite Potential well

In a potential well, the potential energy V(x) will have its minimum. A particle with
its total energy less than the height of the well, will get trapped and is said to exist
in a bound state.
We have V=0, therefore time inde-
pendent Schrödinger equation implies,

&
&
∂ 2 Ψ 2mE
+ 2 Ψ=0 (17)
∂x2 ~ V=0
V
2mE
Let = k2,
~2
∂ 2Ψ
then + k 2 Ψ = 0.
∂x2
x=0 x=L

Solution :
Figure 2: 1D infinite potential well

Ψ(x) = Aeikx + Be−ikx

Boundary conditions : Ψ(x) = 0 at x=0 and x=L

Ψ(at x = 0) ⇒ A+B = 0
⇒ B = -A

Hence, Ψ(x) = 2iAsinkx and,

at x=L we get; 2iAsinkL = 0 ⇒ sinkL = 0 ⇒ kL = nπ.

2π 2πL 2L
We have k = ; so λ = = for n=1,2,3,4,.......
λ nπ n

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 Hence Schrödinger equation for particle in an infinite well, will have its wave-
length in discrete values and a whole number of half-wavelengths will be formed in
the well. They form standing waves.

nπ h nπ nh
• p = ~k = ~ = =
L 2π L 2L
p2 n2 h 2 n2 h 2
• E= = = ⇒ Energy is quantized.
2m 2m × 4L2 8mL2

We have,
Ψn = 2iAsinkx = Csinkx.
Normalizing this, we get
R
|Ψ|2 dx = 1
R
ΨΨ∗ dx =
RL
0
|C|2 sin2 (kx)dx = 1
R L 1 − cos(2kx)
|C|2 dx = 1(18)
0 2
2
R L 1 − cos((2nπ/L)x)
|C| 0 dx = 1
2 Figure 3: Energy levels
R 1 R 1
|C|2 dx − cos((2nπ/L)x)dx = 1
2 2
Let u = 2(nπ/L)x, then du =
2(nπ/L)dx. Hence, we get,
L 1 2nπ
R
2
|C| − cosu × L/2nπdu = 1
2 2 0 R
L L 2nπ
|C|2 − cosudu = 1
2 2 × 2nπ 0
L L
|C|2 − [sin(u)]2nπ
0 = 1(19)
2 2 × 2nπ
L
|C|2 = 1
2r
2
C=
L

r
2  nπx 
Hence, Ψn = sin
L L

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 h2
Energy levels : E1 =
8mL2
⇒ lowest energy level is not ZERO. Hence E1 is called zero-point energy.

Probability density can be estimated by integrating the solution for wave func-
tion;

R R r2  nπx  r
2 ∗ nπx
 
2
P(x) = |Ψn | dx = sin × sin dx
L L L L (20)
2  nπx 
P(x) = sin2 dx
L L
nπx π 3π 5π
P (x) is maximum when = , , etc.
L 2 2 2
If En+1 and En are adjacent energy levels, then the separation between them will
be
h2
∆E = 2
[(n + 1)2 − n2 ]
8mL (21)
h2
∆E ≈ n
4mL2