Origin of Quantum Mechanics

Classical Mechanics
Used to predict the dynamics of material bodies, and
Maxwell’s electromagnetism provided the proper
framework to study radiation; matter and radiation
were described in terms of particles and waves,
respectively.

Classical theory of electromagnetism, and

thermodynamics—made people believe that the
ultimate description of nature had been achieved.
 At the turn of the 20th, however, classical physics,
which had been quite unassailable, was seriously
challenged on two major fronts:

1. Relativistic domain

Einstein’s 1905 theory of relativity showed that the validity of

Newtonian mechanics ceases at very high speeds (i.e., at speeds
comparable to that of light).

2. Microscopic domain

As soon as new experimental techniques were developed to the

point of probing atomic and subatomic structures, it turned out
that classical physics fails miserably in providing the proper
explanation for several newly discovered phenomena.
 Failures of Classical Physics

Microscopic phenomena’s such as

 Blackbody Radiation
 Photoelectric effect
 Atomic stability
 Atomic spectroscopy
The first real breakthrough came in 1900 when Max
Planck introduced the concept of the quantum of
energy.

 Explained the phenomenon of Blackbody radiation

First he was postulated the phenomena of radiation

“as the energy exchange between radiation and its
surroundings takes place in discrete, or quantized,
amounts”.
He argued that the energy exchange between an electromagnetic wave of
frequency (v) and matter occurs only in integer multiples of hv, which
he called the energy of a quantum, where h is a fundamental constant
called Planck’s constant.
Later Planks quantum theory prompted to introduce many concepts
Photoelectric effect
In 1905 Einstein provided a powerful consolidation to Planck’s
quantum concept. In trying to understand the photoelectric
effect, Einstein recognized that Planck’s idea of the quantization
of the electromagnetic waves must be valid for light as well.

Light itself is made of

discrete bits of energy (or
tiny particles), called
photons each of energy hv,
v being the frequency of the
light.
 The number of electrons emitted by a surface
is proportional to the number of incident
photons.

 An electron is emitted as soon as a photon

reaches the surface.

hv = hvo + ½ mV2

φ =hvo = Work function of the material.

½ mV2 = Maximum kinetic energy

Threshold Frequency(vo)

hvo = φ (work function)

hc = φ The minimum amount of energy that has to be

given to an electron to release it from the
λo surface of the material and varies depending
on the material.
λo = Threshold wavelength
The introduction of the photon concept
c = speed of light enabled Einstein to give an elegantly
accurate explanation to the photoelectric
problem, which had been waiting for a
solution ever since its first experimental
observation by Hertz in 1887.
• UV light causes electrons to be released from
the surface of the zinc.
• Emission of electrons commences at the
instant the surface is irradiated.
• The frequency of the radiation must exceed the
threshold frequency.
• Intensity of radiation has no effect.
Prob.1
Copper has a work function of 4.5 eV.
Therefore, the cut-off frequency and
wavelength for light ejecting electrons from
copper?
Work function (Φ) = h vo =h vcutoff
h vcutoff = 4.5 eV, or
vcutoff = 4.5 x (1.6 x 10-19 C)/ 6.63 x 10-34
J-sec
vcutoff = 1.09 x 1015 Hz.

Since λf=c, λ cutoff = c/ vcutoff , or

λ cutoff = (3 x 108 m/s) / (1.09 x 1015 cycles/sec)
= 276 nm (in the UV range)
 Compton Scattering
When light encounters charged particles, the
particles will interact with the light and cause
some of the light to be scattered.

incident
photon scattered
light wave electron photon

electron motion of
electron
after hit
motion of electron
 Compton shift in wavelength

 =scattered-incident= (h/mc)[1-cos(θ)]

 = scattering angle of scattered photon from

the original direction of incoming photon

The scattered photons will have less energy and less

momentum after collision with electrons, and so should
have a larger wavelength according to the formula
 Matter waves (de Broglie hypothesis)

Prince Louis V. de Broglie suggested that massive

particles (i.e. matter) should have wave properties
similar to electromagnetic radiation.
The energy can be written analogous to photons
What applies to mass less particles E = pc = hf, i.e. photons,
also applies to massive particles.
 The wavelength of a matter wave is called the de
Broglie wavelength,
 Postulate 1: State Space
 Any isolated physical space is associated with a
complex vector space (Hilbert space) with inner
product called the State Space of the system.
 The system is completely described by a state vector, a unit
vector, pertaining to the state space.
 The state space describes all possible states the system can be
in.
 Postulate 1 does NOT tell us either what the state space is or
what the state vector is.
Contains (and serves as the basis to extract) all
lΨ(t)> =
the needed information about the system. Any
superposition of state vectors is also a state vector.
 Wave functions that are physically acceptable must, along with their first
derivatives must be finite, continuous, and single-valued everywhere.
 Probability Density

Only the square of its norm, lΨ(r, t)l2 has

meaning. According to Born’s
probabilistic interpretation, the square of
the norm of Ψ(r, t)

P(r, t) = lΨ(r, t)l2

represents a position probability density;
 The Superposition Principle

If Ψ1(r, t) and Ψ2(r, t) separately satisfy the

Schrödinger equation, then the wave function
Ψ(r, t) = α1 Ψ1(r, t) + α2 Ψ2(r, t) , where α1 and
α2 are complex numbers. also satisfies the
Schrödinger equation.

The probability for this superposition.

 Postulate 2: Observables and operators
To every physically measurable quantity A, called an observable or dynamical
variable, there corresponds a linear Hermitian operator  whose eigenvectors
form a complete basis.
Postulate 3: Measurements and eigenvalues
of operators

The measurement of an observable A may be

represented formally by the action of  on a state
vector lΨ(t)>

The only possible result of such a measurement

is one of the eigenvalues an (which are real) of
the operator Â.
 Postulate - 4
 In classical physics it is possible to perform
measurements on a system without disturbing it
significantly. In quantum mechanics, however, the
measurement process perturbs the system significantly.

 While carrying out measurements on classical systems,

this perturbation does exist, but it is small enough that it
can be neglected. In atomic and subatomic systems,
however, the act of measurement induces non-negligible or
significant disturbances.
 Example…………………..
 The electronic orbit is of the order
of 10-10
we must use a radiation whose
wavelength is smaller than 10-10
 We need to bombard the electron
with photons of energies higher than

When such photons strike the electron, not only will they perturb it, they
will knock it completely off its orbit; recall that the ionization energy of
the hydrogen atom is about 13.5 eV. Thus, the mere act of measuring the
position of the electron disturbs it appreciably.
The act of measurement generally changes the state of
the system.

We do not know in advance with certainty in which eigen

state, among the various states , lΨ(t)> a system will be
after the measurement, only a probabilistic outcome is
possible.
 Expectation Values
The expectation value <Â> of  with respect to a
state lΨ(t)> is defined by

For instance, the energy of a system is given by the

expectation value of the Hamiltonian:
 Postulate -5

Time Evolution of the System’s State

Time-dependent Schrödinger equation……………….

 Heisenberg realised that ...

• In the world of very small particles, one cannot measure

any property of a particle without interacting with it in
some way.

• This introduces an unavoidable uncertainty into the

result.

• One can never measure all the properties exactly.

Werner Heisenberg (1901-1976))

 Holds Good for
microscopic particles.
 Also apply for
angular momentum
(∆J) and angle (∆θ).
 Heisenberg’s Matrix Mechanics

1924: de Broglie suggests particles are waves

Mid-1925: Werner Heisenberg introduces Matrix Mechanics

•Semi-philosophical, it only considers observable quantities
•It used matrices, which were not that familiar at the time
•It refused to discuss what happens between measurements
•In 1927 he derives uncertainty principles
Late 1925: Erwin Schrödinger proposes wave mechanics
•Used waves, more familiar to scientists at the time.
•Initially, Heisenberg’s and Schrödinger’s formulations were competing.
•Eventually, Schrödinger showed they were equivalent; different
descriptions which produced the same predictions.
Both formulations are used today, but Schrödinger is easier to understand
 Schrodinger Time independent wave equation

We know that , Wave equation is

In quantum mechanics, y Ψ
(x, y, z)
Ψ

(x, y, z, t)
Particle in a Box

 This model is mainly used as a hypothetical example to

illustrate the differences between classical and quantum systems.
 a particle trapped inside a large box can move at any speed
within the box and it is no more likely to be found at one position
than another.
 However, when the well becomes very narrow (on the scale of
a few nanometers), quantum effects become important.
 Particle in a box (Infinite Square-Well
Potential)
The simplest such system is that of a particle
trapped in a box with infinitely hard walls that
the particle cannot penetrate. This potential is
called an square well potential and is given by:

x=0 x=L x

Clearly the wave function must be zero where the potential is infinite.

Where the potential is zero (inside the box), the time-independent Schrödinger
wave equation becomes:

where

The general solution is:

 Quantization

Boundary conditions of the potential dictate

that the wave function must be zero at x = 0
and x = L. This yields valid solutions for
integer values of n such that kL = nπ.
The wave function is: x
0 L

We normalize the wave function: ½ - ½ cos(2npx/L)

  A  2/ L

The normalized wave

function becomes:

These functions are identical to those obtained for a vibrating string with
fixed ends.
 Quantized Energy

The quantized wave number now becomes:

Solving for the energy yields:

Note that the energy depends on integer values of n. Hence the

energy is quantized and nonzero.

The special case of n = 1 is called the ground state.

PROBLEM In an experiment, an electron is determined to be within
0.1mm of a particular point. If we try to measure the electron’s
velocity, what will be the minimum uncertainty?

SOLUTION

p 
v  
m mx
6.63 10-34 J .s
v 
9.110-31 kg 1.0 10-4 m  2p
v  1.2m / s
Observation:
We can predict the velocity of the electron to within 1.2m/s.
Locating the electron at one position affects our ability to know
where it will be at later times
 Question : An atom in an excited state temporarily stores energy. If the lifetime of this
excited state is measured to be 10 -10 sec, what is the minimum uncertainty in the energy
of the state in eV?
 PROB: An electron is moving along x axis with the speed of
2×106 m/s (known with a precision of 0.50%). What is the
minimum uncertainty with which we can simultaneously
measure the position of the electron along the x axis? Given the
mass of an electron 9.1×10-31 kg
 SOLUTION

From the uncertainty principle: x  p  

We evaluate the momentum:

p  mv  (9.110-31)  (2.05 106 )
p  9.35 10-27 kg.m / s

The uncertainty of the momentum is: x  p  

p  0.5% p  0.5 / 100 1.87 10-24  9.35 10-27 kg.m / s

-34
 6.635  10 / 2p
x 
p   1.13 10-8 m  11nm
- 27
9.35 10
PROBLEM 4 In an experiment, an electron is determined to be
within 0.1mm of a particular point. If we try to measure the
electron’s velocity, what will be the minimum uncertainty?
 SOLUTION

p 
v  
m mx

6.63 10-34 J .s
v 
9.110-31 kg 1.0 10-4 m  2p

v  1.2m / s

Observation:
We can predict the velocity of the electron to within
1.2m/s. Locating the electron at one position affects
our ability to know where it will be at later times.
PROBLEM: A sodium atom is in one of the states labeled
''Lowest excited levels". It remains in that state for an average
time of 1.610-8 s before it makes a transition back to a ground
state, emitting a photon with wavelength 589.0 nm and energy
2.105 eV. What is the uncertainty in energy of that excited state?
What is the wavelength spread of the corresponding spectrum
line?
 SOLUTION

The fractional uncertainty of the photon energy is

PROBLEM 8

An electron is confined to a one-dimensional, infinitely deep

potential energy well of width a = 100pm.
1.What is the least energy (in eV) the electron can have?
2. Compute the energy level of the first excited state, of the
second excited state. Draw the energy level diagram.
SOLUTION

1. The least energy corresponds to the least quantum number:

n = 1 for the ground state. Thus:

h2 (6.625 10-34 ) 2
E1   12
  12
8ma 2
8  9.110-31  (100 10-12 ) 2

6.03 10-18
E1  6.03 10-18 J  -19
E1  37.7eV
1.6 10
2. The energy level of the first excited state corresponds to n = 2:
h2
E2  2  2 2
 4E1 E2  4  37.7eV E2  150.8eV
8ma
The energy level of the second excited state corresponds to n = 3:

h2
E3  2  32
8ma
400
 9E1
2nd excited E3
 9 37.7eV
300
E3  339.3eV
200
1st excited E2
100
Observation:
The levels are not equidistant ground E1
0
 PROBLEM 10

The wave function of a particle confined to an infinitely deep

potential energy well is  ( x)  2 / a sin Kx

The depth of the well is a = 100 pm

What is the probability density of finding the particle at the
distance x = 50 pm for the value of the quantum number
1. n = 1 ?
2. n = 2 ?
SOLUTION

 np 
We have K  np / a  ( x)  2 / a sin  x
 a 
2 2 2  np 
The probability density is  ( x)  sin  x
a  a 
 2  2 p
 ( x)  0.02 sin  x
1. For n = 1: 100  (x: pm)
0.02

2


x
0 50 pm 100 pm

2 2 p
2. For n = 2:  ( x)  0.02 sin  x  (x: pm)
 50 
0.02

2


x
0 50 pm 100 pm