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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 Quantum Mechanics to explain the
atomic energy spectra.

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 wave-particle 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 be found in some region of
space.

Need for Quantum Mechanics


Few limitations of classical mechanics are;
1. The Newtonian Mechanics was not applicable in the region of
atomic and nuclear dimensions.
2. The classical mechanics could not explain the observed spectrum
of black body radiations.
3. This could not explain the observed variation of specific heat of
metals and gases.
4. It was also not able to explain the stability/ instability of the atomic
nucleus.
5. Also, could not explain the origin of discrete spectra of atoms.

In addition to these, there were so many phenomena that


classical mechanics could not explain such as; Photoelectric
effect, Comption effect, Raman effect , etc. These inadequacies
basically open a door for the new branch of physics named as
quantum mechanics

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
ESTABLISHED

PARTICLE NATURE

MATTER WAVE BASED ON


NATURE SYMMETRY

h
mv

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

Motion of electron in H-atom

h = 6.67 x 10-34 Js

h = 6.67 x 10-34 Js

m = 100g = 0.1kg

m = 9.1x10-31kg

v = 30m/s

v = 3 x 107m/s

h 6.67 x10 34
=
=
= 2.22 1034 m
mv
0.1 30

h
6.67x1034
=
=
= 0.24
31
7
mv 9.1x10 x3x10

Since wavelength of golf ball in flight is

The radius of hydrogen atom is R = 0.53

much smaller than size of ball so it shows

which is comparable to . Hence orbiting

particle nature during flight.

electron exhibits wave nature.

VELOCITY OF DE-BROGLIE WAVES


According to de-Broglie, a wave of
wavelength is associated with a
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 massenergy relationship

If vp be the velocity of the deBroglie waves, then

It implies that the velocity of de-Broglie


wave
ave is greater than the velocity of light
w
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.

Hence a material particle cannot


be equivalent to a single wave
train

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 wavepacket 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 effect of the
modulation is thus to produce successive wave groups (wave-packets).

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:
h
2
h
( L)( )
2
h
( 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 interpretation to various physical processes.

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

Pressure & density show space and time variation.

Light

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 at a given position and
time. Hence

( 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

( 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
= Normalizat ion constant
N

Constraints/Properties related to Wave-function:

Schrodinger Equations and its


application

Schrodingers Equation
In order to account for matter waves, Austrian physicist Erwin
Schrodinger in 1926 developed partial differential equations called
Schrodinger equations 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.
Schrodinger equation is the fundamental equation of physics for
describing the quantum mechanical behaviour.
It is a partial differential equation that describes how the wave
function of a physical system evolves over time and space.
It is used to predict analytically the probability of events or outcome
The solution of Sch. Eqn yields quantized energies of the system and
gives the form of wavefunction so that other properties may be
calculated.

Schrodinger equation is the fundamental equation of physics for describing the


quantum mechanical behaviour.
It is a partial differential equation that describes how the wave function of a
physical system evolves over time and space.
It is used to predict analytically the probability of events or outcome
The solution of Sch. Eqn yields quantized energies of the system and gives the
form of wavefunction so that other properties may be calculated.

Time Dependent Schrodinger Equation


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 )

=0

t
t
all space

( 2)

The suitable form of wave function for a particle


moving freely in +x-direction and satisfying the above
condition is

(x, t) = Ae

i(kx t)

2 p
E
k=
=
;
= 2 =
h
h
The matter wave for a free particle
can be represented by the following :
(x, t) = Ae

i
(px Et)
h

(3)

For non-relativistic case,

total energy
=
kinetic
+
potential
,
i.e.
p2
E=
+ V ( x, t )
(4)
2m
From equation (3), we can write:

=
E E = ih
h
t
t
2
2
1 2

2
2
= 2 p
p = h
2
h
x
x 2

(5)
(6)

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

h (x, t)
(x, t)
ih
=
+V (x, t) (x, t)
2
t
2m x
2

This is time dependent Schrodingers equation in one


dimension.

The three dimensional form of Schrodingers equation


is given as:
r
r
r
(r , t )
h2 2 2 2 r
=
ih
2 + 2 + 2 (r , t ) + V (r , t ) (r , t )
t
2m x y z
r
2
r
r
h 2 r
(r , t )
(r , t ) + V (r , t ) (r , t ) = ih
2m
t
h 2
r r
+ V (r , t ) (r , t )

2m

r
(r , t )
= ih
t

r
h2 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 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.

r
r
h2 2 r
(r ) + [E V (r )] (r ) = 0
2m
Hamiltonian of the system is given as :
r
h2 2
H =
+ V (r )
2m
which can be rewritten as :
r
r
H (r ) = E (r )

Steady State Schrodingers Equation


The time dependent form of Schrodingers equation is given as:

( x, t )
h 2 2 ( x, t )
ih
=
+ V ( x, t ) ( x, t )
2
t
2m
x

wave function can also be expressed


as
i

( x, t ) = Ae h

( px Et )

= Ae

where ( x) = Ae

2 =e
x
also,
2

iEt
h

iE
=
e
t
h

ipx
h

(2)
2
x
2

iEt
h

(3)

iEt
h

(1)
ipx
h

=e

iEt
h

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


Schrodingers equation.

h 2 2
+ [E V ( x ) ] = 0
2
2 m x
in 3 D
h2
2 + [E V ( x ) ] = 0
2m

h2 2

+ V ( x) = E

2m

h2 2
for free particle, V ( x) = 0
= E
2m

The 3-dimensional form of this equation is


r
r
h2 2 r
(r ) + [E V ( r )] (r ) = 0
2m
Hamiltonian of the system is given as :
r
h2 2
H =
+ V (r )
2m
which can be rewritten as :
r
r
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

Steady State Schrodingers Equation

State of system is solution


Operator
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


corresponding to operator

quantity

Operators

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

Operand

Result

A =
Operator

Basics of Operators

I = Identity operator
O = 0 Null operator
A =
1

B=A
B =
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

permissible values of physical quantity.

yields

the

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

ih
= E
t

i
( px Et )
h

E ih
t

Momentum Operator with same wave function is given as:

ih
= p
x

p ih
x

Hamiltonian corresponds to total energy of the particle or


system.

h2 2

p2
H=
+ V H
+ V
2
2m
2m x

Angular Momentum Operator corresponding to three


components are:
Lx = ypz zp y
Ly = zpx xpz

Lx ih y z
y
z


Ly ih z x
z
x

Lz = xp y yp x Lz ih 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
h
2mE
If k 2 = 2
h
then we have :
d 2
2
+
k
=0
2
dx

(1)

( 2)

The solution of this differential equation is:

( x) = A sin kx + B cos kx

(3)

Since the particle cant be found outside the


potential well so wave function must obey
boundary conditions:

( x = 0) = 0

( x = L) = 0

(4)

The first boundary condition on wave function


leads to

( x = 0) = B = 0
( x) = ASinkx

(5)

The second boundary condition on wave


function results in
( x = L) = A sin kL = 0
kL = n n = 1,2,....
nx
n ( x) = A sin

n=0 is not allowed, as


Becomes 0  probability of
Locating the particle within the box
vaniishes
Which is against the very
Assumption we started with

Quantization of Energy
The allowed energy values for the particle
obtained from eq. (1) are:
n 2 h 2 n 2 2 h 2
2
En =
=
=
n
E1 (6)
2
2
8mL
2mL

The quantized energies of particle are:


E1 = E1
E2 = 4 E1
E3 = 9 E1
E4 = 16 E1

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 = A 0 sin L xdx = 1
L

A=

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 then all the
states will be of negative energy which is the characteristic of a bound
system.

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 deBroglie 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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