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5-Postulates of Quantum mechanics

The Quantum World (Nottingham Trent University)

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5: Postulates of Quantum
Mechanics
I think I can safely say that nobody understands quantum
mechanics
R Feynman (1965)

Aims:
This section will present the principles of quantum mechanics in a more
mathematical way, as a set of postulates not derived from classical
physics but justified by the experimental verification of their
consequences.
Will be based on so called Copenhagen interpretation (Bohr)

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The wavefunction
Postulate 1: For every dynamical system, there exists a wavefunction that is a
continuous, square-integrable and single valued function of all the particles
coordinates and time and from which all possible predictions of the physical
properties of the system can be obtained.

Coordinates of particles: eg
Single particle moving ( x, t ) Two particles
in one dimension
( x1 , x2 , t )
moving in one
dimension
Single particle moving
(r , t )
in 3 dimensions

Square-integrable: Normalisation integrable is finite

*dV finite

*dV 1
space
For single particles wavefunction is normalised.
space

Wavefunction allows us to know all possible physical properties of the 2


system (everything that is possible to know!)
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Dynamic variables (observables) and operators


Postulate 2a: Every dynamical variable (such as position, momentum.) is
represented by a linear and Hermitian operator

An operator is linear only and only if


For any arbitrary functions 1 and
A c1 1 c2 2 c1 A 1 c2 A 2
2 and constants c1 and c2.

Note: Operators may or may not be differential!

Examples:
Which of the following operators are linear?

A1
A 2 x 1
d
A3
dx
3

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Operators (ctd)
An operator is Hermitian if its expectation (average) value is real ie
A * (r , t ) A (r , t )dV
space
Eigenvalues of Hermitian operators are real.

Recall: Eigenvalue equation

Eigenvalue an of
state n
A n an n
Operator
an real an an*
Eigenfunction n

Eigenvalues of the Hermitian operators are real and thus physically


realisable. In other words that the measured quantities are real .

Eg: Hamiltonian is Hermitian i.e has real eigenvalues

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Operators (ctd)
Most common operators in 1D defined in section 3 pp17-23
Observable Observable Operator Operator operation
name symbol symbol
Multiply by r
x x r ( xi y j z k )
Position r r
1 dimension 3 dimensions
Momentum p p
i i j k
x y z
d
p x i p i i j k
Kinetic K K

2 2 2 2
2 2 2 dx x y z
energy 2m x y z
1 dimension 3 dimensions
Potential U(r) U (r ) Multiply by U(r)
energy

Total E H K U (r )
energy 2 2 2 2 Common observables and
U (r )
2m x 2 y 2 z 2 their corresponding
Angular Lx Lx
quantum operators for a
i y z
momentum z y single particle.
Ly L y
i z x
Measured values of all
x z operators are real.
Lz Lz
i x y
y x
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Properties of linear and Hermitian Operators


Eigenvalue equation: A n an n

Several possible values of eigenvalues an and corresponding eigenfunction n

All eigenvalues are real for all allowed values of n ie an an


*

Eigenfunction are normalised ie:


n*. n dV n dV 1 for all n
2

Different eigenfunctions are orthonormal or orthogonal ie

A m a m m A n an n
m* n dV 0 if n m They do not
overlap in space

Or in a more
condensed form
m* n dV 1 if n m Eigenfunctions are
normalised and
0 if n m orthonormal

Eigenfunctions are said to form a complete set.


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Example: Particle in a box


2 n

Normalised wavefunctions n ( x ) sin x n 1, 2, 3 for 0 x L
L L

Consider 2 lowest states (n=1 and n=2) of particle in a box of width L.

Wavefunctions normalised
2
1 ( x)
sin x
L L
2 2
2 ( x) sin x
L L
It is easy to show both graphically and
analytically that:
L L
2

2
1* 2 ( x) sin x sin x dx 0
L L L
0 0
L
2 mx nx
In general:
m
*
n dx
0
sin sin
L L L
dx 0 if n m

1 if n m 7

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Superposition of eigenfunction
Postulate 3: The linear combinations (superposition) of two or more
eigenfunctions of a given operator may be used to build up a new
wavefunction , which is also a possible state of the system such:
s
c1 1 c2 2 cs s n
cn n Superposition
principle

s may go to and c1,c2cn: coefficients (real or complex)


c1,c2cn: Define composition of the state (r).

Notes:
Each eigenstate n(r) satisfies A n an n

and n form a complete
orthogonal set.
(r) does not have to be an eigenstate of (It is a mixture of eigenstates)

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Superposition Application: Schrdinger's Cat


Cat in steel chamber + Geiger counter with tiny amount of radioactive substance
Within an hour one: equal probability (1/2) of one atom decaying or no one atom
decaying (1/2).
If atom decays, counter triggers and via a relay activate a little hammer which
breaks a container of cyanide killing the cat!
Classical Mechanics: Before measurement, cat can
either be alive or dead.
Quantum Mechanics: Two possible states : dead
and alive at same time
Superposition principle: Wavefunction of cat
before measurement is


1
alive dead
2
Cat is both dead and alive before measurement!
Nature of quantum Reality!

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Schrdinger's Cat ctd


Make measurements: 2 possible outcomes
alive: with probability
dead: with probabilily

Once measurement taken place, wavefunction collapses to either alive or dead

If results of first measurement alive , then result of a second measurement will give alive
again with probability=1.
If results of first measurement alive , then result of a second measurement will give dead
again with probability=1.

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Expansion principle
Postulate 4: Any arbitrary wavefunction can be expanded as a unique
linear superposition of a complete, orthogonal set of eigenfunctions of a
Hermitian operator as:

s
cn n
n
with cn
n*dx

Notes:
has the same boundary conditions as n
Expansions is generalisation of Fourier Series.
Very useful, as can, in principle, any arbitrary wavefunction using
eigenfunctions of whichever observable we want to measure.

Properties: s s
Complex conjugate *: n cn n *
n cn* n*

Normalisation of requires
s s
*dV 1
s s





*
c*m m
c

n n

dV 1 c*
m cn *
m
n dV 1 c*
n cn cn
2
1
m n n, m n 1 n 1
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Expansion (ctd)
s
So if eigenfunctions n constitute a complete set, for wavefunction
to be normalised, it must satisfy: n 1
cn n
s

c
2 2 2
2
1 or in other words c 1 c2 c s 1
Normalised n
n 1

Details in Advanced Modern Physics module (year 3)

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Predicting results of measurements


Postulate 5a: In any measurement of the dynamical variable (observable)
associated with an operator , the only values that will ever be measured are
the eigenvalues an associated with that observable.

Captures the central point of quantum mechanics

Two possible cases:


Case 1: If the system is in an eigenstate ie A n an n
Results of measurement will be eigenvalue an.
Probability associated with measurement pn=1

Example: Take SHO in its ground state 0


Satisfies eigenfunction equation x 2
1
H 0 E0 0 with 0 / 1 / 4 e 2 m E0
2
If the system is in state 0, the only possible result of measuring the
energy of the particle is the corresponding eigenvalue energy E0.
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Measurements (ctd) s
Case 2: If the system is described by a wavefunction
c
n 1
n n
is not an eigenstate of .
What are results of measurements of measuring observable associated with ?
Postulate 5 only eigenvalues of can be obtained
Possible outcomes (results) will be a1, a2 an several possibilities
Associate a probability with each measurement defined as
2
p n c n = probability that the measurement will yield the eigenvalue an
s s

Satisfies
n 1
2
cn 1 pn 1
n 1

The result of a large number of measurements of the observable (average


value)


2 2 2
A * A dV c1 a1 c2 a cn an
s s
A n
2
cn an n
pn an since pn cn
2 Average
value of 14

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Example
Measurement Example: Particle in SHO potential with following wavefunction


( x) c 3 0 ( x) 2 2 ( x) c0 0 ( x) c11 ( x) c2 2 ( x)
0, 1, 2 are 3 lowest states corresponding of the SHO (section 4)
corresponding to n=0, 1and 2 respectively and cn=0 for n3.
Questions:
1. Normalise (x).
2. What are possible values of energy of the particles?
3. Calculate the probability of finding the particle in anyone of the
states 0, 1, 2 Verify that the total probability is equal to 1.
4. Consider an ensemble of 810 identical particles, each of them is
in the state (x). If the measurements are done on all of them,
how many will be found in each of these states?
5. What would be the average value of the energy?
6. Consider two successive measurements. What is the probability
that the first measurement yields E1 followed by E0?

http://www.st-andrews.ac.uk/physics/quvis/simulations_html5/sims/EMeasurement/EMeasurement.html
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Measurement example
Ans:

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Measurements: Collapse of wavefunction


Postulate 5b: Immediately after the measurement, the wavefunction of
the particle is an eigenfunction of the operator corresponding to the
eigenvalue just obtained as the measurement result.

s This is known as the collapse


cn n n of the wavefunction
n 1

If we re-measure the same quantity immediately after first measurement


and would obtain again n (wavefunction collapses to m)
Example: Consider particle in a box with wavefunction ( x)
1
2 1 2
3
If make measurement of energy: 2 possible values either E1 or E2
Assume the result of one measurement is E1, (associated probability p1=2/3)
Question: Assume re-measure energy immediately after the first measurement,
what do we get? What is associated probability What is corresponding
wavefunction?
Ans:

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One other interpretation of QM:

Many-Worlds interpretation (Hugh Everett III 1957)


Wavefunction starts as a superposition.
For each possible measurement outcome a new
world is created!
Denies actuality of collapse of wavefunction!

Entanglement:
Einstein, Podolsky, and Rosen (EPR) paradox, 1935: Paper which argued that
Copenhagen interpretation of Quantum Mechanics is incomplete and suggested existence
of hidden variables.
spooky action at a distance: A measurement of the properties of a particle can have
an instantaneous effect on a measurement of properties of a second particle located
indefinitely far from the first. How could this possibly be? (Einstein, in a letter to M Born
1947).
1936: Schrdinger coined the term entanglement for a pair of correlated quantum
particles that can influence each other instantaneously even if they are large distances
apart.
1964: Entanglement : a Non-local phenomenon (John Bell)
1982: First observation of entangled photon s in decay of excited Ca atoms (Aspect et al,
http://journals.aps.org/prl/pdf/10.1103/PhysRevLett.49.91)
Emerging applications: quantum key distribution, teleportation, clock synchronisation
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Suggested reading: How to teach Quantum Physics to your dog (Chad Orzel)

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Time evolution of a system


Postulate 6: Between measurements (when it not disturbed by any external
influence), the time evolution of the system is described by time dependent
Schrdinger equation: (r , t )
H ( r , t ) i
t
Consider case where Hamiltonian is independent of time. Two cases

1. If n is an eigenstate of
iEn t iEn t
Time dependent wavefunction ( r , t ) n (r ) exp exp gives time dependence


Where n solution of time
H n n (r ) En n (r )
independent SE

s
2. If n is not an eigenstate of but can be expanded as (r ) cn n (r )
s n
Take cn cn (t 0) (r ) cn (0) n (r )
n
s s
Time Evolution (r , t ) n (r )cn (0)e iEnt (r , t ) *n (r )c*neiEnt /
*
n 19
n cn ( t )

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Example
Take previous example of a particle in an SHO potential with wavefunction:

( x)
1
7

2 0 ( x) 3 1 ( x) Wavefunction at t=0

At any time t later wavefunction (x,t),

( x, t )
1
7

2 0 ( x)e iE0t
3 1 ( x)e iE1t

Complex conjugate *(x,t)

* ( x, t )
1
7

2 0* ( x)eiE0t
3 1* ( x)eiE1t

Exercise: Show that

x * ( x, t ) * ( x, t )
2 1
7

4 02 ( x) 3 12 ( x) 4 3 0 ( x) 1 ( x) cosE1 E0 t /

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x * ( x, t ) * ( x, t )
2 1
7

4 02 ( x) 3 12 ( x) 4 3 0 ( x) 1 ( x) cosE1 E0 t /
Ans:

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Summary
Wavefunction to represent state of system .Normalised
Hermitian operators to represent dynamic variables. A n an n
Eigenvalues an are real an an*
Eigenfunctions n are orthonormal

m n dV 1 if n m
*
3D
0 if n m s
(r ) cn n (r )
Superposition of wavefunctions. n
s
Normalisation
cn
2
1
n 1

Only allowed outcomes of measurements are eigenvalues of operator.


Several possible outcomes with associated probabilities.
Probability pn of measurement yielding eigenvalue an pn cn
2

s s
A cn an pn an
2
Average value of observable
Time dependence solution n n
s iEnt
(r , t ) iEn t (r , t ) n (r )cn exp 22
H ( r , t ) i ( r , t ) ( r ) exp
t n
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