The Postulates of Quantum

Mechanics
 Introduction
• The laws of motion formulated by Galileo,
Newton, Lagrange, Hamilton, Maxwell, and
many others, were found to be inadequate to
explain a wide range of phenomena involving
electrons, atoms, and light
• After some efforts, a new theory, “quantum
mechanics” emerged.
• It is now the basic framework for understanding
atomic, nuclear, and subnuclear physics, as well
as condensed-matter (or ”solid-state”) physics.
• A quantum (plural quanta) is the minimum
amount of any physical entity (physical
property) involved in an interaction

• Quantum Mechanics is an axiomatic theory

because it is well-grounded on few principles
(from the Latin principium), or axioms (from
the Greek, axios), or postulates (from the Latin
postulatum), all of these words meaning the
same thing: a truth which doesn’t need any
further proof, because it is obvious by itself
 The Postulates of Quantum Mechanics
The basic questions that quantum mechanics ventures to
answer are the following:
• How can one define the state of a quantum mechanical
system at a given time t?
• How can one represent or describe a measurable
physical quantity (position, momentum, energy,
angular momentum etc) in quantum mechanics?
• How can one calculate the values of various
measurable physical quantities in a given quantum
state?
• Do all possible measurements of an
observable in a given state lead to the same
numerical value? If not, how do we define
the value of an observable in a given state?
• How, knowing the state of the system at
any given instant of time t0, can one
determine the state at any later instant t >
t0?
• The answers to these questions will
eventually lead us to the basic theory of
quantum mechanics.
 Postulate 1
The state of a quantum system at a given
instant of time, t, is completely defined by a
function ψ(r,t), of position r = {x, y, z} and
time, t.

• It is called the wave function of the particle.

• The wave function is a complex-valued
function and contains information about the
position of the particle at time t.
• The wave function ψ(r,t) does not have any
physical meaning of its own.
• However, it has been accepted to consider it as
the probability amplitude in the sense that, if a
measurement of the position of the particle is
carried out, the probability that at a given
instant of time, t, the particle will be found in
an infinitesimal volume element,
ΔV = dxdydz, is given by |ψ(r,t)|2dV.
where

Is a complex conjugate of the wave function,

obtained by replacing any imaginary numbers
with their negative:
• The probability of finding the particle at a
time t near the position (x,y,z) is
proportional to

More precisely, the probability of finding the

particle at time t within a given volume
element dV = dxdydz is:
• The probabilistic interpretation of the wave
function was first developed by Max Born and
it is sometimes referred to as the Born
interpretation of the wave function.
• The wave function must satisfy certain
requirements.
1. It must be a continuous function - There
cannot be points in space where the wave
function is “missing”. There must be a
probability associated with every point in
space.
2. It must be single-valued and bounded
• at a given x,y,z and t, a wave function can
only have one value.
• the value of the wave function cannot be
infinite anywhere
3. It should be normalizable such that the
following integral is equal to one
4. It should have partial derivatives
 Postulate 2
To every observable in classical mechanics there
corresponds a linear, Hermitian operator in quantum
mechanics

• This postulate comes from the observation that the

expectation value of an operator that corresponds to an
observable must be real and therefore the operator
must be Hermitian.
• An operator is an instruction, a symbol which tells us to
perform one or more mathematical acts on a function,
say f(x). The essential point is that they act on a
function.
• Some examples of Hermitian operators are as follows:
 Postulates 3
 In any measurement of the observable
associated with operator Â, the only values
that will ever be observed are the eigenvalues,
a, that satisfy the eigenvalue equation

Where Ψ is the eigen function of the oprator Â,

and a is the eigen value
 Postulate 4
If a system is in a state described by a normalized
wavefunction Ψ, then the average or mean value
of the observable that will be measured
corresponding to the operator A is given by:

This value is called the expectation value

 Postulate 5
The wave function of a system evolves in
time according to the time-dependent
Schrödinger equation

Where T̂ and V̂ are kinetic and potential

energy respectively
 Laws of Quantum Mechanics
• Physics is the branch of science concerned with
the nature and properties of matter and
energy. The definition of physics can be given
as “the study of matter, energy, and the
interaction between them”.
• Physics is then divided into two major category
based upon some of the characteristics. They
are
 Classical theory
 Quantum theory
• The classical theory successfully explained the
motion of an object that is visible to our eyes
or observed by the microscope. It failed to
explain the behavior of atomic particles such
as electron and also about the hydrogen
spectrum, stability of atoms, extra nuclear
space
• In order to overcome the failures of classical
theory, a new theory was proposed which is
mainly based on the concept of photons. This
theory is known as Quantum theory
 Quantum theory
• The quantum theory was proposed by Max Planck
in 1900.
• This theory deals with the body of science
principles that explains the behavior of matter and
its interaction with energy on the scale of atoms
and subatomic particles, mainly with the photons.
• This theory overcome all the failures of the
classical theory and also give rise to new theories
such a s black body radiations, photoelectric effect,
Zeeman effect, Compton effect, absorption and
emission of light
• It deals with the physical phenomena at microscopic
scales, which is in order of Planck constant
• The theories that comes under the concept of
quantum theory are
Black body radiation
Stefan-Boltzmann law
Kirchhoff’s law
Wien’s displacement law
Rayleigh-jeans’ law
Planck quantum theory
Compton effect
Time dependent equation & time independent equation
Schrodinger wave equation
De Broglie wavelength
 Black body radiation

• All objects with a temperature above absolute zero (0

K, -273.15 oC) emit energy in the form of
electromagnetic radiation.
• A blackbody is a theoretical or model body which
absorbs all radiation falling on it, reflecting or
transmitting none.
• It is a hypothetical object which is a “perfect” absorber
and a “perfect” emitter of radiation over all
wavelengths
• The spectral distribution of the thermal energy
radiated by a blackbody (i.e. the pattern of the
intensity of the radiation over a range of wavelengths
or frequencies) depends only on its temperature
• The characteristics of blackbody radiation can
be described in terms of several laws

 Planck’s Law of blackbody radiation A

formula to determine the spectral energy
density of the emission at each wavelength
(Eλ) at a particular absolute temperature (T).
 Stefan–Boltzmann Law
• States that, the intensity of radiation emitted by a
radiating body is proportional to the fourth
power of the absolute temperature of that body
 Wien’s displacement law
• When the temperature of a blackbody
radiator increases, the overall radiated energy
increases and the peak of the radiation curve
moves to shorter wavelengths.
• When the maximum is evaluated from the
Planck radiation formula, the product of the
peak wavelength and the temperature is
found to be a constant.
 The Rayleigh-Jeans Radiation Law
• Was a useful, but not completely successful
attempt at establishing the functional form of
the spectra of thermal radiation.
• The energy density uν per unit frequency
interval at a frequency ν is, according to the
The Rayleigh-Jeans Radiation
 Kirchhoff's law of radiation
• For an arbitrary body emitting and absorbing
thermal radiation in thermodynamic
equilibrium, the emissivity is equal to the
absorptivity.

• Where “E” is the emissive power of a substance

and “a” is its coefficient of absorption
 Planck’s Quantum Theory
• Planck’s quantum theory explains emission
and absorption of radiation.
• Postulates of Planck’s quantum theory are as
follows.
1.Matter radiate energy or absorb energy in discrete
quantities discontinuously in the form of small
packets or bundles. 
2.The smallest bundle or packet of energy is known
as quantum. In case of light, a quantum of light is
known as a photon. 
3. The energy of the quantum absorbed or
emitted is directly proportional to the
frequency of the radiation. So, energy of the
radiation is expressed in terms of frequency
as follows- 
E = hu
4.A body or matter can radiate energy or absorb
energy in whole number multiples of a
quantum as nhv.
• Where n is a positive integer. So, energy can
be absorbed or radiated as hv, 2hv, 3hv,
4hv……etc. not in the form of 1.5hv, 2.5hv…
 Compton effect
• In his 1923, Compton provided the most
conclusive confirmation of the particle aspect
of radiation.
• By scattering X-rays off free electrons, he found
that the wavelength of the scattered radiation
is larger than the wavelength of the incident
radiation
• According to classical physics, the incident and
scattered radiation should have the same
wavelength
• The experimental findings of Compton reveal
that the wavelength of the scattered X-
radiation increases by an amount Δλ, called
the wavelength shift, and that Δλ depends not
on the intensity of the incident radiation, but
only on the scattering angle.
 De Broglie wavelength

• In 1923 de Broglie suggested that wave–particle

duality is not restricted to radiation, but must be
universal: all material particles should also display
a dual wave–particle behavior.
• That is, the wave–particle duality present in light
must also occur in matter
• From the momentum of a photon

we can generalize this relation to any material

particle with nonzero rest mass:
• Each
  material particle of momentum, behaves
as a group of waves (matter waves) whose
wavelength λ and wave vector are governed
by the speed and mass of the particle
 Dirac’s writing
• Splitting the word bracket in two: bra and ket,
Dirac invented a special form of writing,
generally used today in Quantum Theories
• Here is Dirac’s writing: a physical process
starting from an initial state and reaching a
final state is described by the probability
amplitude

 
The vector is the bra vector and | is the ket vector,
observing that the bra vector is the complex conjugate of
the ket vector |final⟩
• Consider, for example, ΨS (n), as being the
probability amplitude of observing the particle
at slit n given that it originated from the source
S (Recall double slit expt)
• We then say that, ΨS (n) is the probability
amplitude of observing the particle at the
position of slit n, given that it was originally at
the position of the source S
• This can be written as,
 Note that,

• for instance, ⟨x|S⟩ is the probability amplitude of

finding the particle at x, i.e. in the state |x⟩, given
that it was initially at the source S , i.e. in the
state |S⟩
• This can also be written as
 Operators in Quantum Mechanics

• Operators such as:

are called “fundamental operators".

• Many operators are constructed from these
operators
• For example the Hamiltonian for a single particle:
• The product of two operators is dened by operating
with them on a function
• Let the operators be  and B, and let us operate on
a function f(x). Then,

is a new function.
• We can therefore say, by the definition of operators,
that AB is an operator which we can denote by C:
• The meaning of ABf(x) should be that B is first
operating on f(x), giving a new function, and then A
is operating on that new function
This means that x is first operating on f(x) and then
p is operating on the function xf(x).
For example

• It is customary to use a short-hand notation

and this is called the commutator of A and B

(in that order).
 Eigenfunctions and eigenvalues of
operators.
• Suppose we have a function f(x) and an
operator Â, then

is a some new function.

• Then we have

• In this case f(x) is called an eigenfunction of Â

and a the corresponding eigenvalue
and since by the de Broglie relation hiskthe
momentum p of the particle, we have
 Linear operators
• An operator  is said to be linear if

where f(x) and g(x) are any two appropriate

functions and c is a complex constant
Hermitian operators.
• and after integration by parts, and recognizing that
the wave function tends to zero as

on the right-hand side

here V is a hermitian operator by virtue of being
a function of the hermitian operator x, and since
T has been shown to be hermitian, so H is also
hermitian
Then,