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Quantum Mechanics

Introduction to Quantum Mechanics,


Group velocity and phase velocity
(No relation)
De-broglie waves, Uncertainty
principle (statement only), Wave
function and its significance,
Normalised wave function
Schrodinger wave equations (Time
dependent and Time Independent)
Particle in a one dimensional box

The Problems with Classical Physics


By the late nineteenth century the laws of physics were
based on Mechanics and the law of Gravitation from
Newton, Maxwell's equations describing Electricity and
Magnetism, and on Statistical Mechanics describing the
state of large collection of matter.
These laws of physics described nature very well under
most conditions, however, some measurements of the
late 19th and early 20th century could not be
understood.

The problems with classical physics led to


the development of Quantum Mechanics and
Special Relativity.

Some of the problems leading to the development of Quantum


Mechanics are listed here.
Black Body Radiation: Classical physics predicted that hot objects would
instantly radiate away all their heat into electromagnetic waves. The
calculation, which was based on Maxwell's equations and Statistical
Mechanics, showed that the radiation rate went to infinity as the EM
wavelength went to zero, ``The Ultraviolet Catastrophe''. Planck solved the
problem by postulating that EM energy was emitted in quanta with .
The Photoelectric Effect: When light was used to knock electrons out of
solids, the results were completely different than expected from Maxwell's
equations. The measurements were easy to explain (for Einstein) if light is
made up of particles with the energies Planck postulated.
Atoms: After Rutherford found that the positive charge in atoms was
concentrated in a very tiny nucleus, classical physics predicted that the
atomic electrons orbiting the nucleus would radiate their energy away and
spiral into the nucleus. This clearly did not happen. The
energy radiated by atoms also came out in quantized amounts in
contradiction to the predictions of classical physics. The Bohr Atom
postulated an angular momentum quantization rule, for , that gave the right
result for hydrogen, but turned out to be wrong since the ground state of
hydrogen has zero angular momentum. It took a full understanding of

Compton Scattering: When light was scattered off electrons, it


behaved just like a particle but changes wave length in the
scattering; more evidence for the particle nature of light and
Plank's postulate.
Waves and Particles: In diffraction experiments,light was shown
to behave like a wave while in experiments like the Photoelectric
effect, light behaved like a particle. More difficult diffraction
experiments showed that electrons (as well as the other particles)
also behaved like a wave, yet we can only detect an integer
number of electrons (or photons).

Quantum Mechanics incorporates a waveparticle duality and explains all of the above
phenomena. In doing so, Quantum Mechanics
changes our understanding of nature in
fundamental ways. While the classical laws of
physics are deterministic, QM is probabilistic. We
can only predict the probability that a particle will

Need for Quantum Mechanics


Few limitations of classical mechanics are;

Wave-Matter Duality
Dual Nature of Light.
De-Broglie Hypothesis.
Matter Waves.
Uncertainty Principle &
Applications.

De-Broglies Hypothesis
COMPOSITION OF UNIVERSE

RADIATION

MATTER

DUAL
NATURE
ESTABLISHE
D

h
mv

PARTICLE
NATURE
MATTER WAVE BASED
ON NATURE SYMMETRY

WAVE PARTICLE DUALITY


DE BROGLIE Hypothesis
In 1924, Louis-Victor de Broglie
formulated the de Broglie hypothesis,
claiming that all matter, not just
light, has a wave-like nature; he
related wavelength, and momentum
as,

Derivation

on the basis of analogy with photons, :

For a particle of zero rest mass,


E=pc, henceforth for photons

de Broglie wavelength relationship applies to other particles


as well.
If instead of a photon, we consider a material particle of
mass m moving with velocity v, then the momentum of the
particle, p = mv

Other expressions..
In terms of kinetic energy

When does a material body exhibits wave


nature ?
Flight of a golf ball
h = 6.67 x 10

-34

Js

m = 100g = 0.1kg
v = 30m/s

h 6.67 x10 34

2.22 10 34 m
mv
0.1 30
Since wavelength of golf ball in
flight is much smaller than size of
ball so it shows particle nature
during flight.

Motion of electron in H-atom


h = 6.67 x 10-34 Js
m = 9.1x10-31kg
v = 3 x 107m/s

h
6.67 x10 34

0.24
31
7
mv 9.1x10 x3x10
The radius of hydrogen atom is R
= 0.53 which is comparable to .
Hence orbiting electron exhibits
wave nature.

According to de-Broglie, a
wave of wavelength is
VELOCITYwith
OF aDE-BROGLIE
WAVES
associated
moving
material particle and is
given by
Let E be the energy of the
particle. Then the frequency
of the wave associated with
a particle is

According to Einsteins
mass-energy relationship

If vp be the velocity of the


de-Broglie waves, then
It implies that the velocity of
de-Broglie wave is greater
than the velocity of light in
vacuum. which is impossible.
Moreover, if the velocity of
the matter wave is greater or
equal to the velocity of light,
then the wave associated
with the particle will move
faster than the particle itself,
thus leaving the particle far
behind.

Wave Packet
Schrodinger postulated that a moving material particle is
not equivalent to a single wave train but equivalent to a
wave packet.
A wave packet consists of a group of waves slightly
differing in their wavelengths, velocities and phases.
these component waves will superimpose in such a way
that the average velocity of component waves is less
than the velocity of light.
The velocity of such wave packet is called group velocity
vg and the velocity of the individual waves forming the
wave-packet is called phase velocity

PHASE AND GROUP VELOCITIES

This equation represents a wave of angular


frequency w and wave number k that has
superimposed upon it a modulation of angular
frequency w/2 and of wave number k/2. The

Expressions for phase and group


velocity
From previous discussion
Phase velocity ,

Group Velocity:

Show that particle velocity is equal to the group wave


velocity?

Duality & Uncertainty Principle


The position of the moving particle is limited
within the span of its associated wave packet.
The broader wave packet is obtained by superposing
harmonic waves having their wavelengths lying in a
narrow interval. Hence position of a particle in such a
wave packet is measurable with large uncertainty while
uncertainty in its momentum is small.
The narrow wave packet is obtained by superposing
harmonic waves having their wavelengths lying in a
broad interval. Hence position of a particle in such a
wave packet is measurable with small uncertainty while
uncertainty in momentum becomes large.
Heisenbergs uncertainty principle is a direct
consequence of wave nature of moving particles.

Generalized Uncertainty
Principles
Various other forms of uncertainty principles
are:

(L)( )
2

(E )(t )
2
(x)(p)

Heisenberg ' s Uncerta int y Pr inciple


Angular momentum Uncerta int y Pr inciple
Einstein' s Time Energy Uncerta int y Pr inciple

Significance of Uncertainty
Principle
These are generalized principles involving a pair of
physical quantities which are canonically conjugate.
The

concerned

uncertainties

are

not

due

to

limitations imposed by instruments or techniques of


measurement but are inherent in nature due to
small value of Plancks constant.
The uncertainty principles play an important role in
providing

alternate

physical processes.

interpretation

to

various

Matter Wave?????
A wave is associated with time and space
variation of a physical quantity.
Sound
variation.
Light

Pressure & density show space and time

E & B fields show space and time variation.

Square of the oscillating physical quantity at a


given position and time is related to the
intensity of wave.


Interpretation of Matter Wave
If we speak with generalization, then propagation of a wave involves a
physical quantity, which varies with position and time. We can illustrate
this with following examples:
Electric and magnetic field vector oscillations in space and time result in
propagating EM waves
The sound waves propagate with variation in pressure in different portion of
media.

In the similar sense, it is of interest to look for the physical quantity


whose space and time variation results in a propagating matter wave.
The interpretation to the matter wave was given by Max Born in
1926. According to him, at any position defined by coordinates (x,y,z)
in the region (where matter wave is spread) and at a given time t, the
absolute square of the amplitude is directly proportional to the
probability of finding the particle at that position at the given time. The
amplitude of the matter wave, also called wavefunction, itself can be a
complex quantity and does not carry any physical meaning.

Wave-function ()

The quantity whose variation constitutes matter


waves is Wave-function. It is denoted by Greek symbol

Representation of Wave-Function: The wave-function


itself has no physical interpretation and can even be a
complex quantity

Representation of Probability: The square of its absolute


value is proportional to the probability of finding the particle
position and time. Hence
at a given
2

( x, y , z , t )

dV P ( x, y, z , t )

Normalized Wave-Function

Mostly it is convenient to have square of absolute value of


wave function at any position and at any time, to be equal to
the probability of finding the particle at that position and time.
For this purpose we proceed as follows:

( x, y, z, t ) dV N
2

( x, y , z , t )

1
( x, y, z , t ) dV 1
N

dV 1

( x, y , z , t )

1
( x, y, z , t ) Normalized Wavefuncti on
N

1
Normalization constant
N

Constraints/Properties related to Wave-function:

Schrodinger Equations and


its
application

Time Dependent Schrodingers Equation


The correct equation for the wave function
(x,t) was discovered by Austrian physicist
Erwin Schrodinger in 1926.
This equation was based on analogy with
classical relation between physical optics
(waves) and geometrical optics (rays). The
waves corresponded to the matter waves
while particle played the role of rays.

For a normalized wave function the probability


interpretation suggests the condition that

( x, t )

dx 1

(1)

allspace

This condition must hold for all times, so derivative


of this condition with respect to time must be zero.

* ( x, t )
( x, t )
*
( x , t ) ( x, t )

t
t
all space

(2)

The suitable form of wave function satisfying


the above condition is
i ( kx t )

( x, t ) Ae
2 p
E
k

;
2

The matter wave for a free particle is :


( x, t ) Ae

i
( px Et )

(3)

total energy is kinetic + potential , i.e.


2

p
E
V ( x, t )
2m

(4)

From equation (3), we can write:

E E i
t

t
2
2
1 2

2
2
2 p
p
2
x

x 2

(5)
(6)

Using (5) and (6) in (4)*, we get:

( x, t )
2 2 ( x, t )
i

V ( x, t ) ( x, t )
2
t
2m x
This is time dependent Schrodingers equation in
one dimension.

The three dimensional form of Schrodingers


equation is given as:

(r , t )
2 2 2 2
i

2 2 2 r , t V (r , t ) r , t
t
2m x y z

2
(r , t )

r , t V (r , t ) (r , t ) i
2m
t


2
V (r , t ) (r , t )

2m

(r , t )
i
t

2 2

V (r , t ) Hamiltonian Operator
2m

Need of Time dependent Schrodinger


Equation
Time-dependent Schrodinger equation is useful when:
The time evolution of the system is important.
The force acting on the system has time dependence.
The steady state Schrodinger equation describes those
systems where acting force has no dependence on time.
Common examples:
o

Electrons motion in atom.

Nucleonic motion in nucleus.

Lattice vibration of atoms.

Steady State Schrodingers


Equation
The time dependent form of Schrodingers equation is given as:
( x, t )
2 2 ( x, t )
i

V ( x, t ) ( x, t )
2
t
2m x

wave function can also ibe expressed as


iEt ipx

( x, t ) Ae

( px Et )

Ae

where ( x) Ae

2 e
x
also,
2

iEt

iE

e
t

ipx

2
( 2)
2
x
iEt

(3)

(1)

e e

iEt

Using (2) and (3) in (1), we get time-independent or steady


state Schrodingers equation.

2 2
E V ( x) 0
2
2m x
in 3D
2
2 E V ( x) 0
2m

2 2

V ( x ) E

2m

2 2
for free particle, V ( x) 0
E
2m

The 3-dimensional form of this equation is

2 2
( r ) E V ( r ) ( r ) 0
2m
Hamiltonian of the system is given as :

2 2
H
V (r )
2m
which can be rewritten as :

H (r ) E (r )

Significance of Schrodingers Equation


This equation is solvable for certain values of E and u(x)
which together define allowed state of the system. Thus
quantization is natural consequence of this equation.
The u(x) is the position dependent wave function also
referred to as eigenfunction . The corresponding value of E
is energy of the system or the eigenvalue.

Using Schrodingers Equation


Microscopic
system: Inputs of
mass, potential &
boundary conditions

Operator

Steady State Schrodingers


Equation
State of system is
solution
Energy
Wave-function : contains all
information of dynamics of system in the
form of probabilities

Expectation
value: most
probable value of
physical quantity

Probable values of physical quantity


corresponding to operator

Operators

What is an Operator ?
Operator is defined as a mathematical instruction
which when acting on a function transforms it.

Operand

A
Operator

Result

Basics of Operators

I
O 0
A

Identity operator
Null operator
B A1

A Eigen equation

Role of Operators in Quantum


Mechanics
The wave function is itself an abstract
function.
However

values

of

physical

quantities

characterizing the state can be extracted by


action of an operator on the wavefunction.
Every Physical Quantity corresponds to an
operator which acting on the wavefunction
yields the permissible values of physical

Operators for Dynamical


Variables

Energy Operator: For a particle moving under


the influence of potential V(x), the wave function
can be expressed as:

( x, t ) Ae

i
E
t

i
px Et

E i
t

Momentum Operator with same wave function is

p
p i
given as: i
x
x

Hamiltonian corresponds to total energy of the


particle or system.

2 2

p2
H
V H
V
2
2m
2m x

Angular Momentum Operator corresponding to


three components are:
Lx ypz zp y
Ly zpx xp z

Lx i y z
y
z


Ly i z x
z
x

Lz xp y yp x Lz i x y
x
y

Particle in Infinitely Rigid Box


Lets consider a particle of mass m trapped
in infinitely deep potential well or an
infinitely rigid box as shown:
V (x)

V (x)

V ( x) 0
X=
0

X=
L

This particle is constrained to be present in


the region 0<x<L as it requires infinite
energy to be in region x<0 or X>L.
The Schrodingers equation applied to the
region 0<x<L of the potential well is
d 2 2mE
2 0
2
dx

2mE
If k 2 2

then we have :
d 2
2

k
0
2
dx

(1)

(2)

The solution
equation is:

of

this

( x) A cos kx B sin kx

differential

(3)

Since the particle cant be found


outside the potential well so wave
function
must
obey
boundary
( x 0) 0
( 4)
conditions:

( x L ) 0

The first boundary condition on wave


function leads to

( x 0) A 0
( x) BSinkx

(5)

The second boundary condition on


wave function results in
( x L)
kL n

n=0 is not allowed, as


Becomes 0 probability of
B sin kLLocating
0
the particle within the
vaniishes
n 1,2,....
Which is against the very
Assumption we started with

nx
n ( x) B sin

Quantization of Energy
The allowed energy values for the
particle obtained from eq. (1) are:
n 2 h 2 n 2 2 2
2
En

n
E1 (6)
2
2
8mL
2mL

The quantized energies of


are:
E1 E1
E2 4 E1
E3 9 E1
E4 16 E1

particle

Allowed Wave Functions


The normalized wave function, whose
absolute square is probability of
particle at a position x in the box, is
2

n
0 x dx B 0 sin L xdx 1
L

2
L

( x)

2
nx
sin
L
L

(7)

Discrete States

E3

E2

E1

3 ( x)

2
3x
sin

L L

2 ( x)

2
2x
sin

L
L

1 ( x)

2
x
sin

L
L

Conclusions

Particle trapped in a rigid box represents a practical situation


of tightly bound electrons in atom or highly bound nucleons
in nucleus.

Such a bound particle can possess only certain quantized


energies.

The state of particle is defined by quantized energy & allowed


wave function.

Probability distribution of this bound particle varies in


different states.

Zero energy is prohibited for a bound particle as it violates


the Heisenbergs uncertainty principle.

If the potential at the surface of the well is taken to be zero

What if the Box is Finitely Rigid ?


Not in syllabus

If box is finitely rigid then probability of trapped particle


being found outside the box is finite although small.

The energy states of such a particle get depressed due to


increased de-Broglie wavelength of the particle.

The particle, with energy lesser than height of well, has


finite although small probability of being found outside too.
This is due to leakage of the particle through the wall. This
phenomenon is called the Tunneling effect.

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