Wave equation and its

significance
Sandhya. S
29.04.2010
HISTORY OF THE ATOM
460 BC
Democritus develops the idea of atoms
he pounded up materials in his pestle and
mortar until he had reduced them to smaller
and smaller particles which he called
ATOMA
(greek for indivisible)
HISTORY OF THE ATOM
1808
John Dalton
suggested that all matter was made up of
tiny spheres that were able to bounce around
with perfect elasticity and called them
ATOMS
HISTORY OF THE ATOM
1898
Joseph John Thompson
found that atoms could sometimes eject a far
smaller negative particle which he called an
ELECTRON
HISTORY OF THE ATOM
Thompson develops the idea that an atom was made up of
electrons scattered unevenly within an elastic sphere surrounded
by a soup of positive charge to balance the electron's charge

1904
like plums surrounded by pudding.
PLUM PUDDING
MODEL
HISTORY OF THE ATOM
1910 Ernest Rutherford
oversaw Geiger and Marsden carrying out his
famous experiment.

they fired Helium nuclei at a piece of gold foil
which was only a few atoms thick.

they found that although most of them
passed through. About 1 in 10,000 hit
HISTORY OF THE ATOM
gold foil
helium nuclei
They found that while most of the helium nuclei passed
through the foil, a small number were deflected and, to their
surprise, some helium nuclei bounced straight back.
helium nuclei
HISTORY OF THE ATOM
Rutherfords new evidence allowed him to propose a more
detailed model with a central nucleus.

He suggested that the positive charge was all in a central
nucleus. With this holding the electrons in place by electrical
attraction

However, this was not the end of the story.
HISTORY OF THE ATOM
1913 Niels Bohr
Proposed that the electrons orbited the nucleus
The further away the more energy was needed.
Electrons only occupy orbits of certain energy.
Bohrs Atom
electrons in orbits
nucleus
Bohrs Assumptions for Hydrogen
The electron moves in
circular orbits around the
proton under the influence
of the Coulomb force of
attraction
The Coulomb force
produces the centripetal
acceleration
Bohrs Quantum Conditions
I. There are discrete stable
tracks for the electrons.
Along these tracks, the
electrons move without
energy loss.
II. The electrons are able
to jump between the
tracks.

In the Bohr model, a photon is
emitted when the electron drops
from a higher orbit (E
i
) to a lower
energy orbit (E
f
).

E
i
-E
f
=hf
Bohrs Model: Energy of the Atom

E =-k
e
e
2
/(2r)

Coulomb constant
Orbit
Elementary charge
The negative sign indicates that the electron is bound to
the proton!
Bohr Model: Orbit Radius
Bohr assumed that the angular momentum of the electron was
quantized and could have only discrete values that were integral
multiples of h/2t, where h is Planks constant
m
e
vr=nh/(2p); n=1, 2, 3,Quantum number
v=nh/(2p m
e
r)

(or principal number)
Bohr Model: Orbit Radius, cont.
It follows:
2
e
2
e
2
2
n
2
2
e
2
2
e
2
2 2
e
2
2
e
2
e
4
4
n
m e k
h
r
r
e k
r m
h n
r
m
r
e k
r
v m
|
|
.
|

\
|
=
=
|
|
.
|

\
|
=
t
t
Bohr orbit radius
Orbital Radii and Energies (for the Hydrogen Atom)
2 2
e
4
2
e
2
n
2
e
2
e
2
2
n
e
1 2
4
2
n h
m e k
E
n
m e k
h
r
r
e k
E
2
|
|
.
|

\
|
=
|
|
.
|

\
|
=
=
t
t
Specific Energy Levels
The lowest energy state is called the ground state
This corresponds to n = 1
Energy is 13.6 eV
The next energy level has an energy of 3.40 eV
The energies can be compiled in an energy level diagram
The ionization energy is the energy needed to completely
remove the electron from the atom
The ionization energy for hydrogen is 13.6 eV
Energy Level Diagram
The value of R
H
from Bohrs
analysis is in excellent agreement
with the experimental value
A more generalized equation can
be used to find the wavelengths
of any spectral lines
Generalized Equation



For the Balmer series, n
f
= 2, n
i
=3, 4, 5,
For the Lyman series, n
f
= 1, n
i
=2, 3, 4,
Whenever an transition occurs between a state, n
i
to another
state, n
f
(where n
i
> n
f
), a photon is emitted
The photon has a frequency f =(E
i
E
f
)/h and wavelength
|
|
.
|

\
|
=
2
i
2
f
H
1 1 1
n n
R

Modifications of the Bohr Theory Elliptical Orbits

Sommerfeld extended the results to include elliptical orbits
Retained the principle quantum number, n
Sommerfeld added the orbital quantum number,
ranges from 0 to n -1 in integer steps
All states with the same principle quantum number are said to
form a shell
The states with given values of n and are said to form a
subshell
BOHR-SOMMERFIELDS MODEL

According to the Bohr-Sommerfeld model, not only do
electrons travel in certain orbits but the orbits have
different shapes and the orbits could tilt in the presence of a
magnetic field. Orbits can appear circular or elliptical, and
they can even swing back and forth through the nucleus in a
straight line.
Heisenberg realised that
In the world of very small particles, one cannot measure any
property of a particle without interacting with it in some way

This introduces an unavoidable uncertainty into the result

One can never measure all the
properties exactly
Werner Heisenberg (1901-1976)
Measuring the position and
momentum of an electron
Shine light on electron and detect reflected
light using a microscope

Minimum uncertainty in position
is given by the wavelength of the
light

So to determine the position
accurately, it is necessary to use
light with a short wavelength
Measuring the position and momentum
of an electron (contd)
By Plancks law E = hc/, a photon with a short wavelength has a
large energy

Thus, it would impart a large kick to the electron

But to determine its momentum accurately,
electron must only be given a small kick

This means using light of long wavelength!
Fundamental Trade Off
Use light with short wavelength:
accurate measurement of position but not momentum

Use light with long wavelength
accurate measurement of momentum but not position


Heisenbergs Uncertainty Principle
The more accurately you know the position (i.e.,
the smaller x is) , the less accurately you know the
momentum (i.e., the larger p is); and vice versa
Classical Physics
Described by Newtons Law of Motion (17
th

century)
Successful for explaining the motions of
objects and planets



In the end of 19
th
century, experimental
evidences accumulated showing that classical
mechanics failed when applied to very small
particles.
) ,..., , (
2
2 1 N
i
i
i
U
m
p
H r r r

+ =
Sir Isaac Newton
The failures of Classical Physics
Black-body radiation
A hot object emits light (consider hot metals)
At higher temperature, the radiation becomes shorter
wavelength (red white blue)
Black body : an object capable of emitting and
absorbing all frequencies uniformly
The failures of classical physics
Experimental observation
As the temperature raised, the peak in the
energy output shifts to shorter
wavelengths.
Wien displacement law


Stefan-Boltzmann law
Wihelm Wien
2 max
5
1
c T = K cm 44 . 1
2
= c
4
/ aT V E = = E
4
T M o =
Rayleigh Jeans law
First attempted to describe energy
distribution
Used classical mechanics and equi-
partition principle



Although successful at high wavelength, it
fails badly at low wavelength.
Ultraviolet Catastrophe
Even cool object emits visible and UV
region
We all should have been fried !
Lord Rayleigh
d dE =
4
8

kT
=
Plancks Distribution
Energies are limited to discrete value
Quantization of energy


Plancks distribution


At high frequencies approaches the Rayleigh-Jeans
law



The Plancks distribution also follows Stefan-
Boltzmanns Las
Max Planck
,... 2 , 1 , 0 , = = n nh E v
d dE =
) 1 (
8
/ 5

=
kT hc
e
hc

kT
hc
kT
hc
e
kT hc

~ + + = 1 ....) 1 ( ) 1 (
/
Wave-Particle Duality
-The particle character of wave
Particle character of electromagnetic radiation
Observation :
Energies of electromagnetic radiation of frequency v
can only have E = 0, h, v 2hv,
(corresponds to particles n= 0, 1, 2, with energy = hv)
Particles of electromagnetic radiation : Photon
Discrete spectra from atoms and molecules can be explained
as generating a photon of energy hn .
E = hv
Wave-Particle Duality
-The particle character of wave
Photoelectric effect
Ejection of electrons from metals
when they are exposed to UV radiation
Experimental characteristic
No electrons are ejected,
regardless of the intensity of
radiation, unless its frequency
exceeds a threshold value
characteristic of the metal.
The kinetic energy of ejected
electrons increases linearly with
the frequency of the incident
radiation but is independent of the
intensity of the radiation .
Even at low light intensities,
electrons are ejected immediately
if the frequency is above threshold.
UV
electrons
Metal
Wave-Particle Duality
-The particle character of wave
Photoelectric effect
Observations suggests ;
Collision of particle like projectile that carries energy
Kinetic energy of electron = h -
: work function (characteristic of the meltal)
energy required to remove a electron from the metal
to infinity
For the electron ejection , h > required.
In case h < , no ejection of electrons
Wave-Particle Duality
-The particle character of wave
Photoelectric effect
Wave-Particle Duality
-The wave character of particles
Diffraction of electron beam from metal
surface
Davison and Germer (1925)
Diffraction is characteristic property of
wave
Particles (electrons) have wave like
properties !
From interference pattern, we can get
structural information of a surface
LEED (Low Energy Electron Diffraction)
Wave Particle Duality
De Brogile Relation (1924)
Any particle traveling with a linear
momentum p has wave length l



Macroscopic bodies have high
momenta (large p)
small wave length
wave like properties are not observed

Matter wave: p = mv = h/
Schrdinger equation
1926, Erwin Schrdinger (Austria)
Describe a particle with wave function
Wave function has full information about the
particle

Time independent Schrdinger equation
for a particle in one dimension
Schrodinger Equation
General form
H+ = E +
H= T + V
: Hamiltonian
operator
The Schrodinger equation:
Kinetic
energy
Potential
energy
+
=
Total
energy
For a given U(x),
what are the possible (x)?
What are the corresponding E?
For a free particle, U(x) = 0, so

(x) = Ae
ikx

E =
2
k
2
2m
Where k = 2t /
= anything real
= any value from
0 to infinity
The free particle can be found anywhere, with
equal probability

The Born interpretation
of the Wave Function
The Wave function
Contains all the dynamic information about
the system
Born made analogy with the wave theory
of light (square of the amplitude is
interpreted as intensity finding
probability of photons)
Probability to find a particle is
proportional to

It is OK to have negative values for wave
function

*
2
= Probability Density
Max Born
Born interpretation of
the Wave Function
Born interpretation of
the Wave Function
Normalization
When is a solution, so is N
We can always find a normalization const. such that the
proportionality of Born becomes equality
1
* 2
=
}
dx N
1
*
=
}
dx
1
* *
=
}
=
}
t d dxdydz
Normalization const. are
already contained in wave
function
Quantization
Energy of a particle is
quantized
Acceptable energy can be found
by solving Schrdinger equation
There are certain limitation in
energies of particles


The information in a wavefunction
Simple case
One dimensional motion, V=0

E
dx
d
m
=
2
2 2
2

ikx ikx
Be Ae

+ =
m
k
E
2
2 2

=
Solution
Probability Density
B = 0
A = 0
A = B
ikx
Ae =
ikx
Be

=
kx Acos 2 =
2 2
A =
2 2
B =
kx A
2
2
cos 4 =
nodes
Eigenvalues and eigenfucntions
Eigenvalue equation
(Operator)(function) = (constant factor)*(same function)


e = O

Eigenfunction
Eigenvalue
Solution : Wave function Allowed energy (quantization)
Operator
= ) observable of (value ) observable to ing correspond (operator
Operators

Position

Momentum

Potential energy

Kinetic energy

Total energy
e = O

x
x
p
2
2
1
kx V =
m
p
E
x
K
2
2
=
V
dx
d
m
V E H
K

2

2
2 2
+ = + =

2
2 2
2

dx
d
m
E
K

=
=
2
2
1

kx V
dx
d
i
p
x

=
= x x
Quantum Numbers
Definition: specify the properties of atomic orbitals and the
properties of electrons in orbitals
There are four quantum numbers
The first three are results from Schrdingers Wave Equation
An atomic orbital is defined by 3 quantum numbers:
n l m
l

Electrons are arranged in shells and subshells of ORBITALS .
n shell
l subshell
m
l
designates an orbital within a subshell

Orbital Quantum numbers
Quantum Numbers
m
l
(magnetic) -l..0..+l Orbital orientation
in space
l (angular) 0, 1, 2, .. n-1 Orbital shape or
type (subshell)
n (major) 1, 2, 3, .. Orbital size and
energy = -R(1/n
2
)
Total # of orbitals in l
th
subshell = 2 l + 1
Symbol Values Description
Quantum Theory Model
Orbitals
One s orbital
Three p orbitals
Five d orbital
Each photon has an energy h, so the total number of
photons needed to produce an energy E is E/h.
The number of photons is
N = E/h
PAt
h(c/)
=
=
PAt
hc
Substitution of the data gives
N =
(5.60 x 10
-7
m) x (100 J s
-1
) x (1.0 s)
(6.626 x 10
-34
Js) x (2.998 x 10
8
m s
-1
)
= 2.8 x 10
20

(1) Calculate the number of photons emitted by a 100 W yellow lamp in 1.0s.
Take the wavelength of yellow light as 560 nm and assume 100 percent
efficiency.
Problems
(2) Show that e
x
is an eigenfunction of the operator d
2
/dx
2
.
What is the eigenvalue?
f(x) = e
x

d
2
/dx
2
(e
x
) = d/dx (e
x
)

=
2
e
x
Thus e
x
is the eigenfunction of the given operator d
2
/dx
2
.

2
is the eigenvalue
(3) Show that e
ikx
is an eigenfunction of a operator
^
P
x
= -ih
/
c
cx
-i
2
k
2
e
ikx
/
= h
F(x) = e
ikx
h
/
c
cx
e
ikx
= -i
/
hk
2
e
ikx
=
Thus eikx is an eigenfunction
(4) For the wavefunction () = Aeim, where m is an integer.
Calculate A so that the wavefunction is normalized

n
*(x)
n
(x) dx = 1
Ae
im
Ae
-im
d =1
= A
2
e
im
e
-im
d = 1
= A
2
=1
Thus A = 1/
}
0
nt
1 - cos2z dx = 1
B
2
a
2nt
B
2
a
2nt
| x - sin2z/2|
0
nt
= 1
Hence B = 2 / a
}
0
a

x
*
= 1
}
0
a
(Bsin ntx/a) (B sin ntx/a) dx =1
} B
2
0
a
sin
2
(ntx/a) dx = 1
(5) For the wavefunction of (x) = B sinnx/a, Evaluate B so that the
wavefunction is normalized. The permitted values of x are 0 x a.