Concepts

in quantum mechanics:

For students: CHEM F213

Superposition of states or superposition principle:

Consider a crystal used as a polarizer. Light polarized along one crystal axis
propagates through the crystal - defined as the parallel direction (||). Light
polarized along the perpendicular () axis doesn't go through.

Figure 2: Polarization axes
||













Classical electrodynamics theory:
|| light goes through the polarizer and light is absorbed or reflected. Light
polarized at an angle to the parallel crystal axis - a fraction cos2 passes
through the polarizer.

Quantum nature of light:
In explaining the photoelectric effect, Einstein put forward the idea that light is
not composed of waves. Light is composed of individual photons. When polarized
light is used in the photoelectric effect - electrons come preferentially in certain
directions. Thus, polarization must be ascribed to individual photons.
A beam of plane polarized light is composed of plane-polarized photons - no
conceptual problem if the photon is polarized either in parallel direction or in
perpendicular direction.
Fundamental problem: For a photon polarized at some angle to the parallel
crystal axis - it is not clear what would be the outcome of an observation?
Quantum mechanics describes observables - questions can only be asked about
the observables.
An experiment is required to explain about the expected outcome for a photon
polarized at some angle to the parallel crystal axis.
Experiment:
i) Photons are incident on the polarizer one at a time.
ii) Place a photodetector after the polarizer.
iii) Photodetector can detect one photon at a time.

Prepared by Shamik Chakraborty, Chemistry Department, BITS-Pilani. August, 2016.
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Concepts in quantum mechanics:

For students: CHEM F213

Quantum mechanics predicts the result:

i) Sometime a whole photon is observed at the detector with the same energy as
that of the incident photon.
ii) Sometime no photon is observed.
When a photon is observed - it is always polarized ||

The photon has somehow jumped from having polarization to the parallel (||).

If the experiment is performed for a large number - cos2 are observed at the
back side of the polarizer.

Superposition of photon states: A photon of polarization , P , is some type of
superposition of the polarization ||, P||, and , P .




P = a P|| + b P
a and b are coefficients - tell how much of each polarization is contained in the
superposition that is P .




The act of observation:
* A photon is reached to the polarizer - an observation is being made as to
whether it is polarized || or .
The act of observation forces the photon state to change entirely into either P|| or
P states of polarization that make up the superposition. The act of observation
causes the photon to make a sudden jump from being partially in each of the
polarizations in the superposition to being in only one.

For one photon: Not possible to conclude which will occur (P|| or P ). Outcome of
many observations yields the classical result: fractioncos2 of the incident
photons has || polarization.

Superposition principle: Whenever a system is in one state, it can always be
considered to be partly in each of two or more states.

Consider a two state system: A and B. Observation of state A yields "a" and same
on state B yields "b":
Observation on a state represented by superposition of A and B will result either
"a" or "b" - never yields anything else. The probability of obtaining result "a" or
"b" in a single measurement depends on relative weights of A and B is
superposition state. This is nothing but related to the coefficients.

Examples:

Prepared by Shamik Chakraborty, Chemistry Department, BITS-Pilani. August, 2016.
Page: 2

Concepts in quantum mechanics:

For students: CHEM F213

H atom in superposition of its 2p and 3p states (You need to know only
Bohr model).
Energy is measured.
In a single measurement either 2p energy or 3p energy will be observed.
An energy will never be observed that is between 2p and 3p energies -
although the state of the system is a superposition of two atomic systems -
one can prepare such state by cooling the atoms first (laser cooling) and
then using narrow band width lasers.
Series of observation on identically prepared atomic size system - result
from one observation to the next in general will vary - enough observation
- probability distribution for the results.
Quantum mechanics provides method to predict/calculate probability
distribution.


Mathematical formulation to translate the superposition principle into the
theory:
In general, superposition implies that the quantum mechanical states are added
together to get a new state of the same system
In polarization phenomenon: P state is being created from P|| and P states.

Mathematical entities* associated with the quantum mechanical states of a
system must also be able to be added together to obtain a representation of the
superposition of state.
Vectors have this property: Any vector can be expressed as the superposition of
three basis vectors (X, Y, Z) **.

Z


R(x, y, z)




X




Y

Vectors have the necessary/required property to be used to represent quantum
mechanical states of a system under investigation. Whatever, we have discussed

Prepared by Shamik Chakraborty, Chemistry Department, BITS-Pilani. August, 2016.
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Concepts in quantum mechanics:

For students: CHEM F213

is only two state systems. In quantum mechanical systems, we may need to deal
with more than 2 or 3 states. Hence, there could be a finite or infinite number of
vectors depending on the requirement of state of the system. In principle, we
need to have a mathematical representation to deal with a vector space whose
dimensionality is specified according the nature of the physical system under
investigation.
In general, such vector space in quantum mechanics is a complex vector space. In
quantum mechanics any physical state is represented by a state vector in a
complex vector space. In normal notation: these physical states are represented
by wave function ().

* You may consider wavefunction () representation of a quantum mechanical state
of the system under investigation. Hence, the example of H atom in last section:
overall = c1 2p + c2 3p.
** These three vectors can be combined using definite combination rules - generate
new basis vectors - capable to represent any general vector (R).

Prepared by Shamik Chakraborty, Chemistry Department, BITS-Pilani. August, 2016.
Page: 4