Quantum Physics - Lecture Notes-ZQ One in One 19 Jan 2011

FE1002 Ph i II FE1002 Physics II
An introduction to An introduction to
Quantum Physics Q y
Associate Professor Zhang Qing g g
Microelectronics Centre
S h l f EEE School of EEE
Nanyang Technological Univeristy
FE1002 Physics II Quantum Physics A/P Zhang Qing (EEE, NTU) 1
Prescribed Text Book
Physics for Scientists and Engineers with Modern
Physics (6
th
Edition)
R A S &J W J tt J R. A. Serway & J. W. Jewett, Jr.
(QC23.S492P 2004)
Main References Main References
University Physics by Hugh D.Young & Roger A Freedman (12
th
Edition) (QC21.2.Y72U 2008)
Fundamentals of Physics (Extended) (7
th
Edition) by D.
Halliday, R. Resnick & J. Walker
(QC21.2H188 2005)
Physics: principles with applications (5
th
Edition)
by Douglas C. C. Giancoli (QC23G433 2005)
Topic One: Introduction p
Isaac Newtonian (1642-1727) developed
the basic concepts and laws of
17
th
1600
the basic concepts and laws of
mechanics and proposed the law of
universal gravitation, etc.
c
s
18
th
1700
i
c
a
l

p
h
y
s
i
c
19
th
James Clark Maxwell (1831 1879)
Dynamic characteristics of an object: position,
velocity, momentum, etc
1700
c
l
a
s
s
i
19
th
James Clark Maxwell (1831-1879)
developed the electromagnetic theory of
light and kinetic theory of gases, etc.
1800
20
th
Characteristics of electromagnetic waves:
wavelength, velocity, amplitude, phase angle, etc.
1900
20
th
1900
A major revolution in physics took place at
the beginning of 20
th
century.
p
h
y
s
i
c
s
In 1900, Max Plank (1858-1974)
introduced the concept of quantum
21
st
m
o
d
e
r
n

p
2000
action.
In 1905 Albert Einstein (1879 1955) In 1905, Albert Einstein (1879-1955)
published his special theory of relativity.
1.1 Background
Topic One: Introduction
g
A few experimental observations could not be
i d i h f k f l i h i
Blackbody radiation
interpreted in the framework of classic physics.
Topic 2
Photoelectric effect
Emission of sharp spectrum
lines from atoms
Topic 3
Topic 5
lines from atoms
New concepts and theories must be introduced.
p
1.2 Wave & particle behavior
In quantum physics, wave and particle are not
contradictory contradictory.
Electromagnetic wave does show
particle characteristics, i.e.,
Electrons and other particles are of
particle characteristics, i.e.,
momentum etc.
Topic 4
wave properties, i.e., wave package
and wave length etc.
Topic 6
The Schrdinger equation with
certain boundary conditions links
the wave and particle properties
Topics 7
&8
the wave and particle properties
together.
& 8
1.3 Applications of quantumphysics
1.3 Applications of quantum physics
Classically, a particle will never overcome a Classically, a particle will never overcome a
potential barrier whose barrier height is larger
than the total energy of the particle. What
about in quantum physics?
Topic 9
about in quantum physics?
Why do we have the periodic table for
different elements?
Topic 10
different elements?
What is the difference between laser light
and ordinary light? How is laser light
Topic 11
and ordinary light? How is laser light
generated?
Topic 11
Topic Two: Blackbody Radiation p y
All objects at temperature T > 0 K emit thermal radiation.
The thermal radiation consists of a continuous
distribution of wavelength from the infrared,
visible and ultraviolet portions of the spectrum visible and ultraviolet portions of the spectrum.
n
s
i
t
y
Mono
S
p
e
c
t
r
a
l

I
n
t
e
n
Mono-
chromator
Detector
As the temperature of an object increases, the major
emitting portion of the spectrum shifts to a shorter
S
emitting portion of the spectrum shifts to a shorter
wavelength.
Topic Two: Blackbody Radiation
2.1 Spectral radiancy
Spectral radiancy or spectral intensity R(,T) tells us
the radiation energy emitted by per unit area of an
p y
object, per unit time, per unit wavelength at a given
temperature T and wavelength . (unit: Js
-1
m
-3
)
Intensity R(,T)d gives the radiated intensity or power
per unit area for the wavelength from to +d. (unit:
Js
-1
m
-2
))
e
n
s
i
t
y
R (,T)
p
e
c
t
r
a
l

i
n
t
e
I(T)
+d
R(,T)d
Figure 2-1: Spectral intensity of an
emitter radiation versus wavelength at
a temperature.
S
p
( )
+d
I t it f t b d t i d b i t ti
Intensity from
1
to
2
can be determined by integrating
in the spectral radiancy with respect to . (unit: Js
-1
m
-2
)
( ) ( )
2
1 2
1
, I T R T d
=
}
(2.1a)
Radiant intensity or power density I(T) is the rediation
energy emitted from per unit surface area of an object in
( ) ( ) d T R T I
}
= ,
(2.1)
gy p j
per unit time for entire wavelength. (unit: Js
-1
m
-2
)
( ) ( ) d T R T I
}
0
,
( )
2.2 Blackbody
2.2 Blackbody
A blackbody is defined as an object that absorbs all the
i id t it
Good approximation of a blackbody is a hole leading
to the inside of a hollow object.
energy incident on it.
A blackbody is also a perfect emitter since an object
in thermal equilibrium emits as much energy as it
absorbs.
Figure 2-2 : The opening to the
cavity inside a hollow object is a
good approximation of a
blackbody.
blackbody.
The radiation of a blackbody depends only on the
The radiation of a blackbody depends only on the
temperature of the blackbody and not on the material
of which the blackbody is made.
The radiation in the
visible region is only a
small portion of the entire
Fi 2 3 S t l i t it f th
small portion of the entire
radiation.
i
n
t
e
n
s
i
t
y
Figure 2-3: Spectral intensity of the
blackbody radiation versus
wavelength (spectral radiancy) at
three temperatures. Note that the 3500 K
S
p
e
c
t
r
a
l

i
p
amount of radiation emitted (area
under the curve) increases with
increasing temperature.
visible region
2.3 The Stefan-Boltzmann law
The Stefan-Boltzmann Law: total radiated intensity
or power per unit surface area of a blackbody is or power per unit surface area of a blackbody is
only determined by the temperature T of the
blackbody as
( )
4
T T I o = (2.2)
where o =5.670 10
-8
Wm
-2
K
-4
is the Stefan-
Boltzmann constant Boltzmann constant.
Ordinary objects radiate less efficiently than a
blackbody and the corresponding radiant intensity
becomes becomes
( )
4
T T I co = (2.3)
where 0<c <1 is the emmisivity of the surface of the
ordinary objects.
For a blackbody, c = 1.
2.4 Wiens displacement law
2.4 Wien s displacement law
max
means the wavelength where the intensity or
radiancy is maximum
Wiens Displacement Law: For a blackbody, the
product of
max
and temperature T is a universal
radiancy is maximum.
p
max
p
constant, i.e,
K m 10 898 . 2
3
max
=

T (2.4)
max
y
Figure 2-4: Wavelength
max
of the
c
t
r
a
l

i
n
t
e
n
s
i
t
y
peak of the curve shifts to shorter
wavelengths at higher temperatures
3500 K
S
p
e
c
2.5 Two classical models
Rayleigh & Jeans Model: assuming that atoms are
h i ill t th t it l t ti t
2.5 Two classical models
harmonic oscillators that emit electromagnetic waves at
all wavelengths, Lord Rayleigh and James Jeans
developed the following formula in 1900;
( )
4
2
,
T ck
T R
B
RJ
=
(2.5)
where k
B
= 1.3810
-23
J/K is Boltzmanns constant and c
is the speed of light.
Eq.(2.5) fits the blackbodys radiation curves well at
long wavelengths (> 50 m), but completely fails at
short wavelengths, because of R
RJ
(,T) as 0.
g ,
RJ
( , )
Wien Model: Wilheim Wien also gave an expression
( )
T
b
W
e
a
T R

=
5
,
(2.6)
based on a conjecture (guess)
( )
W
5
,
( )
where a and b are empirical constants chosen to give the
best fit to the experimental data.
Weins formula fits the curves
well at short wavelengths but
best fit to the experimental data.
g
departs noticeably at longer
wavelengths.
Figure 2-5: Comparison of the Wein
and the Rayleigh-Jeans theories to
that of Planck, which closely follows
the experimental data
the experimental data.
2.6 Plancks model
In 1900, Max Planck, seeking to reconcile these two
laws, made an inspired interpolation which fits the data at
all a elengths all wavelengths.
( )
1 2
,
5
2
=
h
h c
T R
t
(2 7)
( )
1
,
5
T k
hc
B
e

(2.7)
h = ?
(
T k
hc
B
is dimensionless quantity.

T k
B
| |
| || |
| |
1
B
B
k T
k T mJ
h Js
c c ms
(
=
(

| |
Plank adjusted the constant h so that his simulated
curve could perfectly match the observed
blackbodys radiation curves. y
h is Plancks constant: h = 6.626 10
-34
Js
h l f h i i d d f h bl kb d The value of h is independent of the blackbodys
materials and temperatures.
2 7 Plancks two assumptions
Assumption 1: Oscillating atoms/molecules can have
2.7 Planck s two assumptions
only discrete values of energy E
n
, given by
nhf E
n
= (2.8) . . . , 3 , 2 , 1 , 0 = n
where n is called a quantum number and f is the natural
frequency of oscillation of the atoms/molecules.
Radiation energy is quantized.
Each value of n represents a
specific quantum state.
molecule
energy
Figure 2-6: Allowed energy levels
for a molecule that oscillates at its
natural frequency f.
natural frequency f.
Assumption 2: The atoms/molecules emit or absorb
Assumption 2: The atoms/molecules emit or absorb
energy in discrete packets (called photons) by jumping
from one quantum state to another.
D d t iti it
Energy of one photon is the product of h and f:
Upward transition absorbs energy.
Downward transition emits energy.
hc
hf E = =
(2.9)
Energy of one photon is the product of h and f:
where c is the speed of light

in vacuum.
Figure 2-7: A representation
of photons. Each photon
has a discrete energy hf
has a discrete energy hf.
Example 2-1*
Find the peak wavelength of the blackbody radiation
emitted by each of the following objects (as
blackbodies): blackbodies):
(a) The human body when the skin temperature is 35
o
C
(b) The tungsten filament of a light bulb operating at
2000 K
(c) The Sun, which has a surface temperature of about
5800 K
Solution: From Wiens Displacement Law, Eq.(2.4), we
can easily determine
max
as follows
For human body,
( )
m 4 . 9
K m 10 898 . 2
3
max
=
-
=


( )
m 4 . 9
K 35 273
max
+
This radiation of 9.4 m is in the infrared region and

g
invisible to the human eye.
For tungsten filament,
m 4 . 1
2000K
mK 10 898 . 2
3
max
=
It is also in the infrared region so that most of emitted

energy is not visible to us.
For the sun,
5 0
mK 10 898 . 2
3

m 5 . 0
5800K
max
= =
This is near the center of the visible spectrum.
p
2.8 Max Planck (1858 1947)
Max Karl Ernst Ludwig Planck (April 23,
1858 October 4 1947) was a German
2.8 Max Planck (1858 1947)
1858 October 4, 1947) was a German
physicist.
At first Planck considered that the
quantisation was only as a purely formal
assumption ... actually I did not think much
about it ; nowadays this assumption incompatible about it ; nowadays this assumption, incompatible
with classical physics, is regarded as the birth of
quantum physics and the greatest intellectual
li h t f Pl k'
Planck was awarded the Nobel prize for physics in 1918.
accomplishment of Planck's career.
Data Source: http://en.wikipedia.org/wiki/Max_Planck
Topic Three: The Photoelectric
The photoelectric effect: light incident on certain
Effect
p g
metallic surfaces can cause electrons to be ejected
from the surfaces.
Th j d l ll d h l The ejected electrons are called photoelectrons.
The induced current is called photoelectric current.
hf
photoelectrons
Figure 3-1: Photoelectrons
are generated from the
metal
are generated from the
surface of a metal under
impact of an incident light
beam.
Topic Three: The Photoelectric Effect
metallic target
Electron collection
electrode
li d i l
photoelectric current
applied potential
difference
Figure 3-2: An apparatus used to study the photoelectric effect. When a
beam of monochromatic light with appropriate wavelength shines on the
metallic target T photoelectrons will be collected by electrode C and the
metallic target T, photoelectrons will be collected by electrode C and the
photoelectric current i is detected by the ammeter.
3.1 Stopping potential
For a large positive V, the current reaches a maximum
value.
pp g p
The current increases as incident light intensity
increases.
Saturated photo-
electric current
Figure 3-3: Photoelectric current
versus applied potential differences

versus applied potential differences
for two light intensities.
When a negative potential is applied to electrode C
When a negative potential is applied to electrode C,
photoelectrons are repelled, leading to a decrease in
photocurrent.
Stopping potential, V
S
: Any negative bias V < -|V
S
|, no
photocurrent is detectable.
V
S
is independent of radiation intensity, but dependent of V
S
is independent of radiation intensity, but dependent of
the frequency of the incident light.
The maximum kinetic energy of the photoelectrons is
max
| |
s
K q V =
(3.1)
where q=1 610
-19
C is the elementary charge
Classically K
max
should depend on intensity.
where q 1.610 C is the elementary charge.
max
3.2 Cutoff frequency
|V
s
| linearly increases with f
Cutoff frequency, f
0
: any frequency of the incident light
b l f ill h t l t j ti below f
0
will cause no photoelectron ejection.
f
0
is characteristic of the target materials, independent of
radiation intensity.
Classically, effect
should occur at
f
sodium target
any frequency
provided intensity
is high enough.
Figure 3-4: The stopping
potential V
stop
as a function
of the frequency f of the
g g
q y f
incident light.
K
max
increases with increasing light frequency.
Cl i ll K h ld b i d d t f f
Electrons ejected from surface almost instantaneously,
l li h i i i
Classically K
max
should be independent of frequency.
even at low light intensities.
Classically, electrons were expected to require some
time to absorb radiation time to absorb radiation.
Simulation & Illustration
Photoelectric Effect
Key points: This cartoon illustrates the
influences of light intensity, frequency and
bi l h l i bias voltage, etc on photoelectric current.
3.3 Einsteins model
In 1905, Einstein assumed that light of frequency f can
be considered as a stream of photons with energy E be considered as a stream of photons with energy E
given by E=hf [i,e, Eq.(2.9)].
Photon is so localized that it gives all its energy to a single
electron in the metal target.
The maximum kinetic energy of photoelectrons can be
determined by the difference between photon energy
and the work function | (or the minimum energy with
which an electron is bound to the metal), see Fig.3-5. ), g
| = hf K
max
(3.2)
Einsteins model explains the previously mentioned
Einstein s model explains the previously mentioned
features which the classical theory cannot explain.
(1) The effect is not observed below f
0
.
(2) K is independent of the incident light intensity.
The photon energy of incoming photon must be > |.
(2) K
max
is independent of the incident light intensity.
Increasing intensity only increases the number of
photons.
(3) K
max
increases with increasing f.
Kinetic energy of photoelectrons depends only on f.
(4) Th h t l t j t d i t t l (4) The photoelectrons are ejected instantaneously.
Incident energy appears in small packets and there
is a one-to-one interaction between photons and
is a one to one interaction between photons and
electrons.
Electronic energy states in a metal.
Case 1: hf
1
<|, no photoelectrons are ejected.
Case 2: hf
2
=|, the critical case.
Case 3: hf
3
>|, photoelectrons Case 3: hf
3
|, photoelectrons
with certain kinetic energy are
generated.
K
max
E=0
The vacuum
level
|
hf
3
hf
E
F
level
Work function: the
minimum energy
hf
1
hf
2
The Fermi energy
level: the highest
energy level
minimum energy
required to move
an electron from
the metal to
occupied by
electrons at 0 K
vacuum.
Figure 3-5: Electronic
energy states in a metal.
I i l h l i i i
Example 3-1*
In a particular photoelectric experiment, a stopping
potential of 2.1 V is measured when ultraviolet light with
a wavelength of 290 nm is incident on a metal. Using the g g
same setup and metal, determine the stopping potential if
blue light with a wavelength of 440 nm is used, instead of
the ultraviolet light the ultraviolet light.
Solution
34 8
1
19 9
6.66 10 3.0 10
2.1 4.3 2.1 2.2 (eV)
1 6 10 290 10
S
S
hf qV
hf qV
|
|

= +

= = = =

34 8
2
19 9
1.6 10 290 10
6.66 10 3.0 10
2.2 2.8 2.2 0.6 (eV)
1.6 10 440 10
S
qV hf |

= = = =

2
So, 0.6 (V)
S
V =
Example 3-2*
The human eye can respond to as little as 10
-18
J of light
energy. Determine the number of photons that will lead
to an observable flash at a wavelength of 550 nm to an observable flash at a wavelength of 550 nm.
Solution:
18 9
34 8
10 550 10
3
6 6 10 3 10
E E
N
hf hc

= = = ~
6.6 10 3 10 hf hc
3.4 Albert Einstein (1879 1955)
Albert Einstein (March 14, 1879 April 18, 1955) was
a German-born theoretical physicist, one of the greatest
physicists of all time physicists of all time.
He played a leading role in formulating the special and
general theories of relativity, quantum theory and
statistical mechanics.
He was awarded the 1921 Nobel
Prize for Physics for his e o ys cs o s
explanation of the photoelectric
effect in 1905 (his "wonderful
year" or "miraculous year") and year or miraculous year ) and
"for his services to Theoretical
Physics".
Data Source:
http://en.wikipedia.org/wiki/Albert_Einstein
3.5 X-ray photoelectron
X Ph t l t S t (XPS) i
spectroscopy*
X-ray Photoelectron Spectroscopy (XPS) is a
quantitative spectroscopic technique that measures the
empirical formula, chemical state and electronic state of
the elements that exist within a material.
XPS spectra are obtained by irradiating a testing
material with a beam of x-rays while simultaneously
measuring the kinetic energy and number of electrons
that escape from the top 1~10 nm of the material being that escape from the top 1 10 nm of the material being
analyzed.
Figure 3-6: Schematic of an
X-ray photoelectron
spectroscopy.
Figure 3-7: An XPS
spectrum for a testing
sample which contains
Si O C F N Sn etc
Si, O, C, F, N, Sn, etc.
3.6 Photomultiplier tubes*
Photomultiplier tubes (photomultipliers or PMTs) are
extremely sensitive detectors of light in the ultraviolet,
visible and near infrared regions visible and near infrared regions.
0V
500V 500V
1500V
2500V
1000V
2000V
Figure 3-8: Schematic of the
structure of a typical PMT
4500V
3500V
3000V
4000V
5000V
structure of a typical PMT
and a photo of PMTs.
These detectors multiply the signal (number of
electrons) produced by incident light by many times,
from which a single photon could be resolved from which a single photon could be resolved.
The combination of high gain, low noise, high
frequency response and large area of collection frequency response and large area of collection
makes PMTs suitable for applications in nuclear
and particle physics, astronomy, medical imaging
and motion picture film scanning etc and motion picture film scanning, etc.
Topic Four: The Compton Effect
In 1923, A. H. Compton did an experiment that
confirmed the particle-like aspect of electromagnetic
p p
p p g
radiation.
The Compton effect: the scattering phenomenon
associated with incident x ray colliding with electrons associated with incident x-ray colliding with electrons.
Figure 4-1: Comptons
apparatus. A beam of x-
rays of wavelength =
71 1 i di t d t 71.1 pm is directed onto a
carbon target. The
rotating crystal plays a
role of a spectrometer.
p
4.1 Scattering of x-rays
g y
The scattered
x-ray only y y
peak at
0
and
which is a
function of
graphite
0
o
90
o
function of
the angle.
Classically, the
45
o
graphite
135
o
y
wavelength of the
scattered x-ray is a
broad distribution
incident
x-ray
0
Figure 4-2: Scattering of x-ray as the function of
135
o
broad distribution
at a given angle.
Figure 4-2: Scattering of x-ray as the function of
the angle with respect to the incident direction.
4.2 Scattering of electrons
The electron is scattered through an angle | with
respect to the incident photon as if this was a billiard-
ball t pe collision ball type collision.
Figure 4-3: Illustration of the scattered x-ray
and electron in the Compton effect.
Classically, the electron would be pushed along the incident
direction due to radiation pressure and set into oscillatory
direction due to radiation pressure and set into oscillatory
motion driven by the waves oscillating electric field.
4.3 Comptons model
To fully explain the effect, Compton and his co-workers
had to treat photons, not as waves, but rather as point-
p
had to treat photons, not as waves, but rather as point
like particles assuming that the energy and momentum
of any colliding photon-electron pair are conserved,
respectively respectively.
The energy of photons E = hf [Eq.(2.9)] and the
t
(4.1)
h hf
p = =
momentum
(4.1)
c
p
Using these ass mptions and the la s of energ
Using these assumptions and the laws of energy
conservation and momentum conservation in both x and
y directions, he derived the Compton Shift Equation;
( ) u cos 1 '
c 0
=
(4.2)
where and
0
are the scattered and incident light
wavelength, respectively, as indicated in Fig.4-3.
= h/m c=0 00243 nm is called the Compton
c
= h/m
e
c=0.00243 nm is called the Compton
wavelength, m
e
=9.10910
-31
kg is the rest mass for
electron and c is light speed in vacuum.
Comptons measurements were in excellent
agreement with his predictions and these really
convinced physicists of the fundamental validity of
Photon transferred energy to the electrons during
convinced physicists of the fundamental validity of
the quantum theory.
collision and hence the scattered x-ray has a longer
wavelength.
The unshifted peak (
0
) is due to scattering from the The unshifted peak (
0
) is due to scattering from the
atoms tightly bound inner electrons which do not gain
significant energy from incident photons.
Example 4-1*
p
A 1.010
-12
m wavelength photon collides with a free
electron initially at rest. After the collision, the photon
recoils directly backward. (i) Determine the wavelength,
momentum and energy of the scattered photon and (ii)
determine the momentum and kinetic energy of the de e e e o e u a d e c e e gy o e
scattered electron.
Solution:
=180
o
f f
Figure 4 4: Illustration of momentum of the scattered photon and
0
, f
0
, f
Figure 4-4: Illustration of momentum of the scattered photon and
electron in the Compton effect.
Solution:
From Eq.(4.2), we have the wavelength of the scattered
photon
( ) ( )
( )( )
( )
0 c
34
12 o
' 1 cos
6.626 10 J s
1.0 10 1 cos180
u
= +
-
= +
( )( )
( )
31 8 1
12 12 12
1.0 10 1 cos180
9.11 10 kg 3.00 10 m s
1.0 10 4.8 10 =5.8 10 (m)

+
-
= +
The momentum and energy of the scattered photon:
34
22
6.6 10
1 1 10 (k / )
h

'
22 8 14
1 1 10 3 0 10 3 3 10 (J)
hc
E p c

' '
= = = =
22
12
6.6 0
1.1 10 (kgm/s)
5.8 10
ph
h
p
'
= = =
'

1.1 10 3.0 10 3.3 10 (J)
ph ph
E p c
= = = =
'
From momentum and energy conservation, we have:
h h
0
e
h h
p

'
= +
'
e ph e ph
E E E E
'
+
'
= +
0
0
Therefore, the momentum and kinetic energy of the
and
34
12 12
0
1 1
6.6 10
1.0 10 5.8 10
e
h h
p

| |
'
= + = +
|
'

\ .
, gy
scattered electron are:
0
22
1.0 10 5.8 10
7.7 10 (kgm/s)

\ .
=
0 0
1 1
k h h
E E E E E hc
| |
' '
= = =
| 0 0
0
34 8 13
12 12
1 1
6.6 10 3.0 10 1.6 10 (J)
1 0 10 5 8 10
k e e ph ph
E E E E E hc

|
'
\ .
| |
= =
|
\ .
12 12
1.0 10 5.8 10
|

\ .
Note: according to classic physics
( )
( )
2
2 22
7 7 10
p

'
( )
( )
13
classic
31
7.7 10
3.3 10 (J)
2 2 9.1 10
e
k
e
p
E
m

= = =

Wrong!
4.4 A. H. Compton (1892-1962) p ( )
Arthur Holly Compton (September
10th, 1892 - March 15th, 1962)
discovered the Compton effect, which
clearly illustrates the particle concept
of electromagnetic radiation, was of electromagnetic radiation, was
afterwards substantiated by C. T. R.
Wilson who, in his cloud chamber,
could show the presence of the tracks could show the presence of the tracks
of the recoil electrons.
For this discovery, Compton was awarded the Nobel y p
Prize in Physics for 1927 (sharing this with C. T. R.
Wilson).
D t S
Data Source:
http://nobelprize.org/nobel_prizes/physics/laureates/1927/compton-bio.html
Topic Five: Atomic Spectra
Low-pressure gas subject to electric discharge emits
discrete line spectrum (emission spectra)
p p
discrete line spectrum (emission spectra)
Mono-
chromator
Detector
Figure 5-1: Emission line spectra for hydrogen, mercury and neon.
Absorption spectrum is obtained by passing light from
Absorption spectrum is obtained by passing light from
a continuous source through the gas or dilute solution.
Absorption spectra of low pressure gases show a series
of discrete dark lines superimposed on a continuous
spectrum of light source.
Mono-
chromator
Detector
White light
Figure 5-2: Absorption spectrum for hydrogen gas.
5.1 Hydrogen emission line series
In 1884, Johann Balmer realized that the wavelengths
of the first 4 lines in the visible spectrum of hydrogen
y g
p y g
were related by
5 4 3
1 1 1
|
|
|
R . . . 5, 4, 3,
1
2
1 1
2 2
H
=
|
.
|
\
|
= n
n
R
(5.1)
h R 1 097 10
7 1
i ll d h R db where R
H
= 1.09710
7
m
-1
, is called the Rydberg
constant.
1/ is called wavenumber.
Other series of lines in hydrogen were soon found and
Other series of lines in hydrogen were soon found and
Balmers equation was generalized.
1 1 1
| |
. . . 2, 1, ,
1 1 1
2 2 1
2
1
2
2
H
+ + =
|
|
.
|
\
|
= n n n
n n
R
(5.2)
B l i f 2 ( i ibl ) Balmers series for n
2
= 2 (visible)
Lymans series for n
2
= 1 (UV)
Paschens series for n
2
= 3 (IR)
All of these equations were purely empirical. No
Bracketts series for n
2
= 4 (IR)
theoretical basis existed for them.
Classic electromagnetic theory could not explain
these.
these.
5.2 The Bohr atom
In 1913, Niels Bohr proposed an atomic theory that
accounted for the spectra lines of hydrogen. The model
contains:
(1) The electron moves in circular orbits around the
proton under the influence of the Coulomb force of proton under the influence of the Coulomb force of
attraction.
Figure 5-3: Diagram represent- g g p
ing Bohrs model of a hydrogen
atom, in which the orbiting
electron is allowed to be only
in specific orbits
in specific orbits.
(2) Only certain orbits are stable i e electrons in these (2) Only certain orbits are stable, i.e, electrons in these
orbits do not emit or radiate energy.
In classical physics, orbiting electrons should In classical physics, orbiting electrons should
continuously radiate, losing energy and causing it to
spiral into the nucleus.
(3) Radiation is emitted when electrons jump from a
more energetic initial orbit to a lower energy orbit.
Frequency of the emitted radiation depends on the Frequency of the emitted radiation depends on the
difference between the energy of the initial state, E
i
,
and the energy of the final state, E
f
and E
i
> E
f
.
hf E E
f i
= (5.3)
(4) The allowed orbits are those for which the electrons
bi l l b h l i
orbital angular momentum about the nucleus is an
integral multiple of = h/2t.
n vr m
(5 4)
n vr m
e
=
(5.4)
Using these four assumptions, the allowed energy levels
f h d b l l d of a hydrogen atom can be calculated:
3 2 1
1
2
=
|
|
|
= n
e k
E
e
(5 5)
. . . 3, 2, 1, ,
2
2
0
=
|
.
\
= n
n a
E
n
(5.5)
where k
e
=1/(4tc
0
)=8.98810
9
Nm
2
/C
2
is the Coulombs
constant and a
0
= h
2
/[m
e
k
e
(2te)
2
]= 0.0529 nm is the Bohr
radius, which corresponds to the orbit with the smallest
radius.
radius.
R di f ll d bit i
0
2
a n r
n
=
(5.6)
Radius of any allowed orbit is
Fi 5 4 Th fi h Figure 5-4: The first three
circular orbits predicted
by the Bohr model of the
hydrogen atom.
y g
With Eq.(5.5), we have the energy of hydrogen:
eV
606 . 13
2
n
E
n
=
(5.7)
. . . 3, 2, 1, = n
Only energies satisfying Eq. (5.7) are permitted.
n = 1 is the ground state with E
1
= -13.606 eV. g
1
V
n = 2 is the first excited state with E
2
= -3.401 eV.
n = is the free electron state with E
= 0 eV.
The energy needed to completely remove an electron
from the atom in its ground electronic state is called
the ionization energy the ionization energy.
The ionization energy for hydrogen is
E
-E
1
=13.6 eV
Frequency of the photon emitted when electron jumps
Frequency of the photon emitted when electron jumps
from an outer orbit i to an inner orbit f can be
determined from Eqs.(5.3) and (5.5):
|
|
.
|
\
|
=
=
2 2
0
2
1 1
2
i f
e
f i
n n h a
e k
h
E E
f
(5.8)
. \
f
The wavenumber or 1/ is:
|
|
|
2
1 1 1 e k f
|
|
.
|
\
|
= =
2 2
0
1 1
2
1
i f
e
n n hc a
e k
c
f
(5.9)
R
H
Comparing Eq.(5.9) with Eq.(5.2), the Rydberg constant is
1 - 7
2
H
m 10 097 . 1 = =
e k
R
e
(5 10)
0
H
2 hc a
(5.10)
The theoretical
The theoretical
Rydberg constant is
accurate to within 1%
of the experimentally
determined value.
The spectra series for The spectra series for
hydrogen can be
interpreted as
IR
transitions between
the energy levels.
visible
Figure 5-5: An energy level
di f h d
diagram for hydrogen
UV
5.3 Niels Bohr (1885-1962)
( )
Niels (Henrik David) Bohr (October 7,
1885 November 18, 1962) was a , )
Danish chemist who made
fundamental contributions to
understanding atomic structure and understanding atomic structure and
quantum mechanics. Bohr is widely
considered one of the greatest
h i i f h i h physicists of the twentieth century
(even though he self-identified as a
chemist). )
He received the Nobel Prize for Physics for his atomic
theory in 1922.
Data Source: http://en.wikipedia.org/wiki/Niels_Bohr
Topic Six: Wave-Particle Duality Topic Six: Wave-Particle Duality
Blackbody experiments, photoelectric effect, Compton
effect and atomic spectra offer ironclad evidence that
when light and matter interact, they behave like
particles. particles.
A photon has a speed of c, energy of hf=hc/ and
momentum of hf/c=h/ and no mass. f
On the other hand, light and other electromagnetic waves
exhibit interference and diffraction effects which could
be interpreted only with wave characteristics.
Electromagnetic wave has its amplitude, frequency and
phase angle.
Q Which model (particle or wave) is more appropriate?
Topic Six: Wave-Particle Duality
A. Depends on the phenomenon observed some
experiments are better or solely explained using
Q. Which model (particle or wave) is more appropriate?
experiments are better or solely explained using
particle model while others are better or solely
explained using wave model.
Light has a dual nature. It exhibits both wave
and particle characteristics and particle characteristics.
To understand why photons are compatible with electro-
magnetic waves, let us consider a radio wave and x-ray.
Consider a 2.5 MHz radio wave (=120 m).
Its energy E =hf ~ 10
8
eV too small to be detected.
Requires a lot of photons to produce a detectable signal
At higher frequencies energy of photon is higher and
q p p g
graininess is lost.
At higher frequencies, energy of photon is higher and
graininess can be easily detected.
For very high frequencies such as x-ray and -ray, the
photons are easily detected as a single event, but wave
effects are difficult to observe.
6 1 The Wave properties of particles 6.1 The Wave properties of particles
In 1923, L. V. de Broglie, in his doctoral dissertation,
postulated that because photons have wave and postulated that because photons have wave and
particle characteristics, perhaps all forms of matter
have wave as well as particle properties.
Electrons have particle-wave nature electrons in
motion exhibit wave properties. motion exhibit wave properties.
From the momentum wavelength relationship of p=h/
From the momentum-wavelength relationship of p=h/
for photons, de Broglie applied this relation to other
particles.
de Broglie wavelength: de Broglie suggested that
material particles of momentum p are associated with
their characteristic wavelength :
mv
h
p
h
= =
(6.1)
their characteristic wavelength :
The frequencies of the matter waves obey the Planck
relationship
mv p
relationship.
h
E
f = (6.2)
h
Example 6-1*
If a proton and an electron have the same de Broglie
wavelength, will they have the same kinetic energy?
Account for your answer If not determine the ratio of the Account for your answer. If not, determine the ratio of the
protons kinetic energy to that of the electron.
S l i Th h diff ki i i
2
2
1
|
.
|
\
|
= =
h p
E
e
k
Solution: They have different kinetic energies

2 2
|
.
\
m m
k
31
2
10 1 9
2
1
|
.
|
\
|
h
m E
4
27
31
2
10 5 . 5
10 7 . 1
10 1 . 9
2
1
2

= =
|
.
|
\
|
. \
=
p
e
e
p
electron k
proton k
m
m
h
m
m
E
E

2
. \
e
m
6.2 Louis de Broglie (1892-1987)
6.2 Louis de Broglie (1892 1987)
Louis-Victor-Pierre-Raymond, 7th
duc de Broglie, generally known duc de Broglie, generally known
as Louis de Broglie (August 15,
1892March 19, 1987), was a
French ph sicist French physicist.
He introduced his theory of
electron waves. This included the electron waves. This included the
wave-particle duality theory of
matter. For this he won the Nobel
Prize in Physics in 1929 Prize in Physics in 1929
Data Source: http://en.wikipedia.org/wiki/Louis, 7th duc de Broglie
Data Source: http://en.wikipedia.org/wiki/Louis,_7th_duc_de_Broglie
6.3 Double-slit experiment
p
If de Broglies hypothesis is right, we should observe
the interference pattern caused by a beam of electrons
incident to double slits.
The experimental requirements: the slit width<< the p q
separation between the two slits; the detector is far
behind the slits.
The experimental procedures: (1) Close one slit and
only leave the other open for a given time and
observe the pattern. (2) Open the both slits at the observe the pattern. (2) Open the both slits at the
same time for the given time.
Figure 6-1: The two blue curves in the middle represent the patterns of
individual slits with the upper or lower slit closed.
Figure 6-2: The single blue curve on the right represents the accumulated from
the two blue curves. The brown curve represents the interference pattern with
both slits open at the same time.
p
Particles through double slits
Key points: This simulation shows
interference patterns for a beam of particles
i th h d bl lit Th i fl passing through double slits. The influences
of slit width and particle mass on the
patterns can be seen.
Example 6-2*
A particle of charge q and mass m has been accelerated
from rest through a potential difference AV. Show its
d B li l th h/(2 AV)
1/2
de Broglie wavelength =h/(2mqAV)
1/2
.
Solution: when a charged particle is accelerated from rest
through a potential difference AV the gain in kinetic through a potential difference AV, the gain in kinetic
energy mv
2
/2 must equal the loss in potential energy qAV
p 1
2
2
AV
m
p
mv V q
2 2
1
2
= = A
where the momentum p=mv=(2mq AV)
1/2
v=0
v
where the momentum p=mv=(2mq AV)
1/2
,
so that
V
h h
A
= =
2
Shown!
V mq
p
A 2
6.4 Determination of the wavelength
I 1927 C J D i d L H G d d i
6.4 Determination of the wavelength
of electron
In 1927, C. J. Davisson and L. H. Germer succeeded in
measuring the wavelength of electrons.
I th i t In their apparatus,
electrons are
accelerated from a
hot filament
heated filament F by
an adjustable potential
difference V.
Figure 6-3: The apparatus
used in the Davisson-Germer
difference V.
experiment.
The electron beam with kinetic energy of eV, is
i id i k l l C
incident to a nickel crystal C.
A detector at D at an angle | reads the current I of
electrons entering the detector for various potential electrons entering the detector for various potential
difference V.
There is a strong diffracted beam at | = 50 and V = 54
Figure 6-4: The results obtained by Davisson and Germer for five different
accelerating voltages, shown as polar plots of current I as a function of the angle |.
There is a strong diffracted beam at | 50 and V 54
V but not otherwise.
Figure 6-5: A simplified
representation of a nickel representation of a nickel
crystal.
|
Dsin|
The crystal surface acts like a diffraction grating with
i D spacing D.
Because of the low energy of the electrons, they cannot
penetrate very far into the crystal and diffraction takes
penetrate very far into the crystal and diffraction takes
place in the plane of atoms on the surface.
This situation is very similar to light reflected from
This situation is very similar to light reflected from
diffraction grating where the maxima must satisfy the
following equation.
. . . 3, 2, 1, sin = = m D m |
(6.3)
For nickel crystal, D = 2.15 and m = 1,
we have = D sin50
o
=1.65.
Since the kinetic energy of the electrons is gained from
electric potential acceleration E
ke
=p
2
/2m=eV, we can have
the classic momentum p=(2eVm)
1/2
and the de Broglie the classic momentum, p (2eVm) and the de Broglie
wavelength is =h/p=h (2eVm)
-1/2
=1.6710
-12
m=1.67 .
In 1928, G. P. Thomson of Scotland also observed
electron diffraction patterns by passing electrons through
thi ld f il very thin gold foils.
These results show conclusively the wave nature of
electrons and confirmed de Broglies hypothesis. electrons and confirmed de Broglie s hypothesis.
Q Would the wavelengths of 10 eV photon, electron and
t b th ? proton be the same?
6.5 Principle of complementarity p p y
The dual nature of matter and radiation is conceptually
difficult to understand because the two models seem to
contradict each other.
Neils Bohrs principle of complementarity states that
th d ti l d l f ith tt
Q How do they complement each other?
the wave and particle models of either matter or
radiation complement each other.
Q. How do they complement each other?
Position of particle can be localized in both space and
time but a wave cannot, being spread out in both of time but a wave cannot, being spread out in both of
these dimensions.
6.6 Uncertainty principle
Localizing a wave in space and considering wave at
arbitrary instant t = 0.
|
|
.
|
\
|
=
0
2
cos
tx
b y
2b
. \ 0
2b
0
2
0 0
2 4
, 0, 0 k k
t t

A
= A A ~
x =
0
k =0
b
Figure 6-6: (a) A harmonic wave viewed at t = 0. (b) The distribution
f b h l t f th lit d f th h i
of wave numbers, shown as a plot of the amplitude of the harmonic
component as a function of its wave number.
The wave can be expresses as:
The wave can be expresses as:
( )
|
|
.
|
\
|
=
=0
2
cos ,
x
b t x
t
(6.4)
. \ 0
where b is a constant.
This wave has a sharply defined wavelength and a
corresponding sharply defined wave number k
0
= 2t/
0
Ak or Ak=0.
If this wave is to represent a particle, the uncertainty Ax
i th i i i fi it (i h l th i ) in the x axis is infinite (i.e. anywhere along the x axis).
Add sine or cosine waves with properly chosen wave
numbers amplitudes and phases see Fig 6 7(b) and
numbers, amplitudes and phases, see Fig.6-7(b), and
sum up all the waves over, we have a wave packet only
over a certain region Ax and zero everywhere else,
Fig.6-7(a).
x
2b
0
2
0 0
2 4
, 0, 0 k k
t t

A
= A = A ~ =
x
b
Figure 6-7: (a) A wave packet of length Ax, viewed at t = 0. (b) The
relative amplitudes of the various harmonic components that combine to
make up the packet. The central peak has a width Ak.
Length of waves Ax & width of wave number Ak
Key points: Through the Fourier
transform, this illustration shows clearly
that wave number (k=2t/) distribution
becomes broad when the length of the
wave reduces. wave reduces.
Wave is now localized, but purity of the wave is
sacrificed since the packet contains a spread of wave
numbers (Ak) centered about k
0
. u be s ( k) ce te ed about k
0
.
Hence the sharper the wave packet (or smaller Ax), the
broader the range of wave numbers (Ak) we must use to
In general, as Ax increases, Ak decreases. The
f ll i l ti hi h ld
build up the wave packet and vice versa.
following relationship holds
1 ~ A A x k (6.5)
Form de Broglie wavelength Eq.(6.1), we have
x
p
p
k A =
|
|
|
A =
|
|
|
A = A
t t t 2 2 2
(6.6)
x
p
h h
k A =
|
.
\
A =
|
.
\
A = A
(6.6)
A l i E (6 5) th Applying Eq.(6.5), then
1
2
~ A A = A A x p
h
x k
x
t
(6.7)
h
2
h
x p ~ A A
(6 8)
or
t 2
x p
x
A A
(6.8)
Taking into account that momentum is a vector and for
id l i
non-ideal instruments,
t 4
h
x p
x
> A A
t
t
4
4
h
h
y p
y
x
A A
> A A
(6.9)
t 4
h
z p
z
> A A
These are the mathematical formulations of the
Heisenberg Uncertainty Principle for position-
momentum relation.
Though an individual measurement of momentum of a
Though an individual measurement of momentum of a
particle can yield an arbitrarily precise value, that value
can be anywhere in a range Ap
x
about the true p
x
.
Repeated measurements on identically prepared systems
generate results clustered about p
x
with statistical
di ib i f id h A
It is not possible to determine both the position and
th t f ti l ith li it d i i
distribution of width Ap
x
.
the momentum of a particle with unlimited precision.
Observing a wave at x = 0.
g
( )
|
|
.
|
\
|
'
=
=
0
0
2
cos ,
T
t
b t x
x
t
(6.10)
where T
0
is the period and the angular frequency is
defined as e
0
(= 2t/T
0
) and b is a constant.
If this wave has a sharp angular frequency of e
0
= 2tf
0
,
it must be a continuous harmonic for infinite time t, see
Fi 6 8 Fig. 6-8.
t
2b
T
0
t =
0
Ae = 0
b
0
e
0
e
0
e
0
e
0
e
b
Figure 6-8: (a) A harmonic wave viewed at x = 0. (b) The distribution
of angular frequencies, shown as a plot of the amplitude of the harmonic
component as a function of its angular frequencies.
component as a function of its angular frequencies.
Similarly, add sine or cosine waves with properly
chosen angular frequency e, amplitudes and phases and
sum up all the waves over, we have an impulse only
over a certain duration At and zero beyond it. over a certain duration At and zero beyond it.
If the duration At will decrease, the spread of angular
frequencies Ae will increase. Thus we have:
1 ~ A A t e (6.11)
As the energy of the particle is E = hf the uncertainty in
As the energy of the particle is E hf , the uncertainty in
frequency is related to the uncertainty in energy.
E
f
A
= A (6 12)
h
f = A (6.12)
Substitute Eq.(6.12) into Eq.(6.11) with Ae = 2tAf=
2tAE/h, 2tAE/h,
t 2
h
t E ~ A A (6.13)
The following
is the Energy-Time Uncertainty Relationship
g
t 4
h
t E > A A
(6.14)
It is not possible to determine both the energy and the
time coordinate of the particle with unlimited precision
is the Energy-Time Uncertainty Relationship.
time coordinate of the particle with unlimited precision.
ll i i h i
All energy measurements carry in inherent uncertainty.
The lowest state of an atom (ground state) has well
defined energy because the atom normally exists gy y
indefinitely in that state.
All other states at higher energies are less precise
because the atom (sooner or later) will move
spontaneously to a lower energy state.
Example 6-3* p
The speed of an electron is measured to be 5.0010
3
m/s
to an accuracy of 0.00300%. Find the minimum
uncertainty in determining the position of this electron.
Solution: The momentum of the electron is
m/s kg 10 56 . 4 10 00 . 5 10 11 . 9
27 3 31
- = = =

mv p
x
The uncertainty in p
x
is 0.00300% of this value, so
Ap
x
=0.00003004.5610
-27
kgm/s. From Eq.(6.9),
38 0 00038 0
10 626 . 6
34
A

h
mm 38 . 0 m 00038 . 0
10 368 . 1 14 . 3 4
10 626 . 6
4
31
= =

=
A
> A

x
p
h
x
t
6.7 Werner Heisenberg (1901 1976)
Werner Karl Heisenberg
(December 5, 1901 February 1,
g ( )
1976) was a celebrated German
physicist.
He invented matrix mechanics the He invented matrix mechanics, the
first formalization of quantum
mechanics in 1925. His
i i i l d l d i uncertainty principle, developed in
1927, states that the simultaneous
determination of two paired p
He received the Nobel Prize in physics in 1932
quantities, has an unavoidable uncertainty.
Data Source: http://en.wikipedia.org/wiki/Heisenberg
Topic Seven: A Particle in a 1-D
Box
7.1 Wave function and probability
Wave function + is a mathematical expression
(usually a complex quantity) to describe the waves
i i l
p y
representing particles.
If we know the wave function + (x, y, z, t) for every point
in space and every instant of time we know all about the
Probability density is determined by |+ |
2
(probability
in space and every instant of time, we know all about the
behavior of the particle.
per unit volume, or area, or length), defined as the
probability of experimentally finding the particle
described by the wave function at x, y, z at time t.
y , y,
Probability that the particle will be somewhere must be
Topic Seven: A Particle in a 1-D Box
Probability that the particle will be somewhere must be
equal to unity (100% chance of finding it) in the space.
1
2
= +
}
dV
(7 1) (normalization condition)
1 = +
}
dV
(7.1) (normalization condition)
To normalize a wave function is to multiply it by a
constant such that Eq (7 1) is satisfied
For a one-dimension system, where the particle must be
located along the x axis and its wave function is only a
constant such that Eq.(7.1) is satisfied.
located along the x-axis and its wave function is only a
function of x, we replace dV with dx and
2
}
( ) 1
2
= +
}
dx x (7.2)
Figure 7-1: The probability of a
particle being in the interval ax
b is the area under the curve
from a to b.
Probability of finding the particle in the interval a s xsb
is
dx P
b
a
ab
}
+ =
2
(7.3)
Expectation value of a particles position x (for 1 D
Expectation value of a particle s position x (for 1-D
case) is determined by
dx x x
}
+ =
2
(7 4)
dx x x
}

+ =
(7.4)
The expectation value a particles position x is the p p p
average value of x. Once the wave function is known,
it is possible to calculate the average position x or the
expectation value of the particle
In general, the expectation value of a function f(x) is
expectation value of the particle.
( ) ( ) dx x f x f
}

+ =
2
(7.5)
7.2 A particle in a 1-D box
Classically, if a particle is confined to moving along the
x-axis and bouncing back and forth between two
impenetrable walls with a speed of v, then its momentum
(mv) and its kinetic energy are constants.
Figure 7-2: A particle of mass
m and velocity v confined to m and velocity v confined to
moving parallel to the x axis
and bouncing between two
impenetrable walls.
7.2.1 The wave function of the particle
Quantum mechanics approach to this problem is very
different and requires that the appropriate wave function
consistent with the conditions of the situation be found consistent with the conditions of the situation be found.
If a string of length L is fixed at each end, the standing
waves set up in the string must have nodes at two ends.
y(x)=0
y(x)=0
Figure 7-3: Standing
waves set up in a stretched
string of length L.
y(x)=0
g g
x=0 x=L
R hi d l h l th i i t l
Resonance achieved only when length is some integral
multiple of half-wavelengths.
2
or
n
L
L n

(7 6)
n = 1 2 3 or
2
n
n
L n
n
= =
(7.6)
n = 1, 2, 3, . . .
The standing waves are only the form of stable waves
whose wavelengths are quantized whose wavelengths are quantized.
( ) ( )
2 x t
| |
For the standing waves, it can be shown that
( ) ( )
2
sin sin
n
n
x
y x A k x A
t
| |
= =
|
\ .
(7.7)
where A is the amplitude. Substitute Eq.(7.6), we have
( )
|
.
|
\
|
=
L
x n
A x y
t
sin
(7.8)
For a particle in a 1 D box of length L the de Broglie
For a particle in a 1-D box of length L, the de Broglie
waves of the particle, in analogy with standing waves on
a string, must form standing wave.
( )
|
|
|
= +
x n
A x
t
sin
(7.9)
n = 1 2 3
The allowed wave functions for the particle is
Allowed de Broglie wavelengths are those of standing
( )
|
.
\
= +
L
A x sin
( )
n = 1, 2, 3, . . .
waves
n
=2L/n.
( ) 0
(x)=0
|(x)|
2
=0
(x)=0
(x)=0
|(x)|
2
=0
|(x)|
2
=0
|(x)|
2
=0
Figure 7-4: The first three allowed states for a particle confined to a one-
dimensional box. (a) The wave functions for n = 1, 2, and 3. (b) The
probability distributions for n = 1 2 and 3
probability distributions for n 1, 2, and 3.
7.2.2 The probability density of the particle
The probability density: |+|
2
+ can be either positive or negative, but |+|
2
is always p g y
positive.
|+|
2
is zero at the boundaries, in other words, it is
i ibl t fi d th ti l t th i t impossible to find the particle at these points.
Where|+|
2
is the maximum and zero depends on n.
Th b bili d i di ib i i h i The probability density distribution is shown in
Fig.7-4(b).
7.2.3 The energy of the particle
The kinetic energies of the allowed (stable) states are
( ) 2
2
2 2
L h
gy p
( )
2
2
2 2
2
2
2 2
| |
= = =
h
m
L nh
m
p mv
E
n
(7.10)
3,.... 2, 1, n
8
2
2
=
|
|
.
|
\
|
= n
mL
h
E i ti d ith th Energy is quantized with the
lowest energy corresponding
to n = 1 (zero-point energy).
Figure 7-5: Energy level diagram for a
particle confined to a one-dimensional
particle confined to a one dimensional
box of width L. E
1
=h
2
/8mL
2
.
Cl i ll th i i f th ti l
Classically, the minimum energy of the particle can
be zero.
When a particle drops from E
3
to E
2
, it emits a photon
of energy hf = E
3
E
2
.
It l b b h t d j f E t E if It can also absorb a photon and jumps from E
1
to E
2
if
the incident photon has energy hf = E
2
- E
1
.
Topic Eight: Schrdinger Equation Topic Eight: Schrdinger Equation
8 1 1 D ti
General form of the wave equation for waves traveling
along the x axis
8.1 1-D wave equation
along the x axis
( ) ( )
2
+
=
, +
t
t x
v x
t x
c
c
c
c , 1
2
2 2
2
(8.1)
t v x c c
where + and v are the amplitude and propagation speed
of the wave.
In quantum mechanics, particles behaviors can described
using de Broglie waves, which should satisfy Eq.(8.1).
8.2 A system with constant energy
Topic Eight: Schrdinger Equation
We consider an isolated bound system and the paticles
interaction inside it is ignorable, the total energy E = hf g gy f
of the particle will remain constant.
The wave function of the de Broglie waves is
l t t di t i b
( ) ( ) ( ) t x t x e cos = , +
(8.2)
analogous to standing waves on a string can be
expressed as
( ) ( ) ( ) t x t x e cos ,
( )
Substituting into Eq.(8.1),
( )
( )
( ) ( ) t
x d
t
|
|
|
|
2 2
cos cos e
e
e ( )
( )
( ) ( )
( )
( )
x d
t x
v x d
t
|
|
|
|
|
.
\
=
2
2 2
2
cos cos
e
e e
(8 3)
( )
( ) x
v x d
x d
|
|
.
|
\
|
=
2 2
e
(8.3)
or
Recall that e = 2tf = 2 tv/ and p = h/, then
2
2
2
2
2
2
2
2
4 2
p
p
h v
= =
|
.
|
\
|
=
t
t e
(8.4)
. \
E th t t l f ki ti (K) d
where =h/2 is the reduced Planck constant.
Express the total energy as sum of kinetic (K) and
potential energy (U).
2
p
E K U U
( )
2
2
2
p
E K U U
m
p m E U
= + = +
=
(8.5)
( )
(8.6)
( )
e
2
2
2
2 2
2
v
p m
E U = =

and
v
Substituting Eq (8.6) into Eq (8.3), we have
(8.7)
( )
( ) ( ) ( ) x E x x U
x d
x d
m
= +
2
2 2
2
kinetic
energy
potential
total energy
This is 1-D time-independent Schrdinger Equation.
For 3-D time-independent Schrdinger Equation;
energy
energy
( ) ( ) ( )
z
z y x
y
z y x
x
z y x , , , , , ,
2
2
2
2
2
2
+ +
c
c
c
c
c
c
( ) ( ) ( ) z y x z y x U E
m
y
, , , ,
2
2
=
(8.8)
In principle, if U(x,y,z) and two appropriate boundary
conditions are known, we can solve the Schrdinger
equations to obtain the wave functions and energies
equations to obtain the wave functions and energies
for the allowed states.
Example 8-1*
A free electron has a wave function (x)=Aexp(ikx),
where x is the position and k is a constant. (i) Show that
its non relativistic kinetic energy may be expressed as its non-relativistic kinetic energy may be expressed as
( )
m
k
E
2
2
=
e
m 2
where is the reduced Planck constant and m
e
is the rest
mass of electron.
Solution:
For free electron, U=0. The time-independent Schrdinger
equation: equation:
( )
( )
2
2
2
2
d x
E x
m d x
=
2m d x
d
ik
= Since
2
2
2
ik
dx
d
k
dx
=
Since
dx
Substituting the above into the time time-independent
Schrdinger equation, we have
( )
( ) ( )
2
2
2
k x E x
m
=
g q ,
2m
So
( )
2
k
h
( )
2
e
E
m
=
shown
8.3 Erwin Schrdinger (1887-1961)
8.3 Erwin Schrdinger (1887 1961)
Erwin Rudolf Josef Alexander
Schrdinger (August 12, 1887 Schrdinger (August 12, 1887
January 4, 1961), an Austrian
physicist, achieved fame for his
contributions to quantum contributions to quantum
mechanics, especially the
Schrdinger equation.
He received the Nobel Prize in
1933 for his great contributions.
Data Source: http://en wikipedia org/wiki/Schrodinger
Data Source: http://en.wikipedia.org/wiki/Schrodinger
8.4 Determination of
8.4 Determination of
The solutions + to the Schrdinger Equation should
satisfy the following conditions: satisfy the following conditions:
Since it is second order differentiation equation, one
must need two boundary conditions to determine the
wave function.
At the boundary of two contiguous regions, the wave
function must join smoothly at the boundary between function must join smoothly at the boundary between
regions. For 1-D at the boundary x=x
0
,
( ) ( ) x x x x =
(8 9)
( ) ( )
( ) ( ) x x d x x d
x x x x
+
+
=
0 0
0 0
(8.9)
(8.10)
dx dx
+ (x) must obey normalization condition :
+ (x) must obey normalization condition :
( ) 1
2
=
}

dx x
(8.11)
( ) 0 = x
(8.12)
(x) must be single-valued and must also be
Note : Steps leading to Eq (8.7) do not represent a
(x) must be single-valued and must also be
continuous for finite values of U(x).
derivation of the Schrdinger Equation. Rather, the
procedure represents a plausibility argument based upon
an analogy with other wave phenomena that are already an analogy with other wave phenomena that are already
familiar to us.
8.5 An example-a particle in a 1-D
8.5 An example a particle in a 1 D
box revisited
Figure 8-1: Diagram of a one-
dimensional box of width L and
infinitely high walls.
The1-D
impenetrable
box is a 1-D
infinite
infinitely high walls.
Potential energy distribution:
U(x) = for x s 0 and x > L
potential well
U(x) for x s 0 and x > L
U(x) = 0 for 0 < x <L (8.13)
The particle does not feel any external forces exerted to it.
Thus, the particle can never escape from the box and
(x) = 0 for x s 0 and x > L (8.14)
(x) 0 for x s 0 and x > L (8.14)
I id th b 0 < < L th S h di E ti
Inside the box 0 < x < L, the Schrdinger Equation
Eq.(8.7) becomes
mE d 2
2
(8.15)
mE
k
mE
dx
d
2
2
2
2 2
= =
(8 16)
h
mE
k
2
=
(8.16)
where
The general solution to Eq.(8.15) is g q ( )
( ) ( ) ( ) kx B kx A x cos sin + =
(8.17)
h A d B t i t ti t t t b where A and B are two integration constants to be
determined as follows
Using the boundary condition, Eq.(8.14),(0)=0, we
Applying the other boundary condition, Eq.(8.14),
Using the boundary condition, Eq.(8.14),(0) 0, we
have B=0
( ) 0 sin = kL A
(8.18)
(L)=0, we have
We have to require sin(kL)=0 This requirement leads to
We can not require A=0. Otherwise, =0 everywhere.
We have to require sin(kL) 0. This requirement leads to
t n kL
n=1, 2,3. (8.19)
Substituting k in Eq (8 19) into Eq (8 17) we have the
Substituting k in Eq.(8.19) into Eq.(8.17), we have the
final wave functions, see Fig.8-2:
( )
|
.
|
\
|
=
x n
A x
n
t
sin n=1, 2, 3. (8.20) ( )
|
.
\
L
n
, , ( )
Applying the normalization condition Eq.(8.11):
2
1 sin
0
2
=
|
.
|
\
|
}
dx
L
x n
A
L
t
1
(8.21)
2
1
2
|
.
|
\
|
=
L
A
Th b bili d i Fi 8 2(b) i The probability density, see Fig.8-2(b), is
( ) | |
|
.
|
\
|
=
L
x n
L
x
n
t
2
2
sin
2
n=1, 2,3. (8.22)
. \
L L
With Eq.(8.16) and Eq.(8.19), we have obtained the
(8 23) t n L
mE
kL = =
2
n = 1 2 3
energy of the particle, see Fig.8-3:
(8 24)
2
2
h
E |
|
|
(8.23) t n L kL = =
n = 1, 2, 3, . . .
(8.24)
2
2
8
n
mL
E
n
|
.
\
=
These results agree with those obtained in the previous These results agree with those obtained in the previous
section.
(x)=0
|(x)|
2
=0
(x)=0
(x)=0
|(x)|
2
=0
Fi 8 2 Th fi t th ll d t ti t t
|(x)|
2
=0
Figure 8-2: The first three allowed stationary states
for a particle confined to a one-dimensional box.
(a) The wave functions+ for n = 1, 2, and 3. (b)
the probability densities |+|
2
for n = 1, 2, and 3. p y , ,
Figure 8-3: Energy level diagram for a particle
confined to a 1-D box of width L. The lowest
allowed energy is E = h
2
/8mL.
Example 8-2*
p
A 1.00 mg object is confined to moving between two
rigid walls separated by 1.00 cm. Calculate the
i i d f h bj minimum speed of the object.
Solution: The minimum speed corresponds to the state
for which n=1 From Eq (8 24) for which n 1. From Eq.(8.24),
( )
J 10 49 . 5
01 . 0 10 1 8
10 63 . 6
8
58
2 6
2
34
2
2
1

=

= =
mL
h
E
01 . 0 10 1 8 8mL
This energy corresponds to kinetic energy of the object,
/ 10 31 3
10 49 . 5 2
/ 2
26
2 / 1
58
|
|
|

E m/s 10 31 . 3
10 1
/ 2
26
6
1

=
|
|
.
\

= = m E v
The speed is so small that it can be considered to be at
rest, which is what one would expect for the minimum
speed of a macroscopic object!
Example 8-3*
A particle confined to a 1-D infinite potential well
from x=0 to x=+L has a wave function given by
2
sin
n x
L L
t
| |
+ =
|
\ .
determine the probability that it will be found between
(1) x=0 and x=L/4, (2) x=L/4 and x=L/2, (3) x=0 and x=L/2
2
2 1 2
sin 1 cos
n x n x
dx dx
L L L L
t t (
| | | |
=
| |
(
\ . \ .

} }
Solution:
Since
1 2
sin
2
L L L L
x n x
L L
t
| |
(
\ . \ .

| |
=
|
\ .
} }
2 L n L t
|
\ .
Yielding:
2
/ 4
/ 4
0 / 4
0
0
2 1 2
sin sin
2
t t
t
(
| | | |
= =
| |
(
\ . \ .

}
L
L
L
n x x n x
P dx
L L L n L
0
1 1
sin
4 2 2
t
t
\ . \ .

| |
=
|
\ .
n
n
2
/ 2
/ 2
/ 4 / 2
/ 4
2 1 2
sin sin
2
t t
t
(
| | | |
= =
| |
(
\ . \ .

}
L
L
L L
L
n x x n x
P dx
L L L n L
/ 4
2
1 1
sin
4 2 2
t
t
t
\ . \ .

| |
= +
|
\ .
L
L L L n L
n
n
\ .
2
1
2 / 4 / 4 / 0 2 / 0
= + =
L L L L
P P P
2
8.6 Characteristics of the
particle in the box
Classically the particle would be expected to stay still Classically, the particle would be expected to stay still
with zero kinetic energy at very low temperatures.
In quantum mechanics, the particle cannot be at rest in
the box.
The stable wave functions (standing waves) are
caused by multiple reflections of the particles de y p p
Broglie wave at the two walls of the box.
Zero-point energy is the lowest energy (ground state)
d 1 d corresponds to n = 1 and
E
h
1
2
2
8
= (8.25)
mL
1
2
8
Depending on the quantum state n, the electron spends
p g q , p
more time at certain position of the box than in others.
In the ground state, the electron is more likely to be
f d th t th it ll Thi fi di found near the center than near its walls. This finding
contradicts classical theory.
As n increases, the distribution of electron probability , p y
density becomes more uniform and approaches
classical theory.
8.7 Finite potential well
V
0
=
p
0.5 n=3
0.3
0.4
V
0
=0.3 eV
0.2
E
/
e
V
n=2
0.1
n=1
5
-5
0.0
x/nm
x/nm
Fi 8 4 T i l ll f ( ) i fi i d h d (b) fi i d h (0 3
Figure 8-4: Two potential wells of (a) infinite depth and (b) finite depth (0.3
eV), respectively, are compared. The wells have the same width of 10 nm.
The following characteristics can be found when we deal
g
with the more realistic case of a finite quantum well:
1) Note that=0 at the two walls of the well. It
should satisfy boundary conditions Eqs. (8.9) and
(8.10). As a result, there is a spilling over of the
exponential tail of the probability curve. p p y
2) The energy levels E
n
are lower than the
corresponding ones in the infinite deep quantum
ll ith th ll idth
3) If the particle energy is higher than the barrier height
V
0
, it will not be trapped. If lower, it may be trapped
well with the same well width.
0
, pp , y pp
with a probability of escaping from the trap. It is
also possible to find the particle beyond the well.
Quantum well of finite height
Key points: Influences of the well height,
width and particle energy on the wave p gy
functions, energy of the states, etc are
illustrated.
Topic Nine: Tunneling p g
9.1 Tunneling through a rectangular
b i barrier
Consider a particle of energy E incident on a rectangular
barrier of finite height U and width L where E<U barrier of finite height U and width L, where E<U.
Classically, the particle must be
reflected as it does not have reflected as it does not have
sufficient energy to overcome the
barrier. U
E
In quantum mechanics, the
amplitude of the de Broglie wave
associated with the particle is
L
E
p
nonzero everywhere.
Tunneling or barrier penetration: the possibility of
Topic Nine: Tunneling
finding the particle on the far right side of the barrier.
Figure 9-1: for a particle
incident from the left on the
b i f h i ht U i barrier of height U is
sinusoidal in regions I and
III, but exponentially
decaying in region II. y g g
The probability of tunneling can be described with a
transmission coefficient T and a reflection coefficient R.
1 R T
1 = + R T
(9.1)
9.2 Transmission coefficient of
tunneling
T i i ffi i t f t li T i th Transmission coefficient of tunneling T is the
probability that the particle penetrates the energy barrier.
An approximate expression for T (when T <<1) is
( )
(
E U m L 2 4t ( )
(
(
~
h
E U m L
T
2 4
exp
t
(9.2)
h h i Pl k t t d E th d where h is Plancks constant, m and E are the mass and
energy of the incident particle, L and U are the width
and barrier potential height, respectively.
Quantum Tunneling
Key points: We pay our attention to the
waveforms of incident, penetrated and
reflected de Broglie waves and the
influences of U, L and E on them.
9.3 Low contact resistance
th h t li *
through tunneling*
For a metal in contact with
highly doped semicon-
ductor N
D
>10
19
cm
-3
, the
barrier width becomes
very narrow, the tunneling
current becomes dominant
and contact resistance R and contact resistance R
C
decreases rapidly with
increased doping.
Figure 9-2: Calculated and measured
values of specific contact resistance.
Upper insert shows the tunneling
L i h h i i
process. Lower insert shows thermionic
emission over the low barrier.
9.4 Scanning tunneling microscope*
g g p
An electrically conducting
probe with a very sharp tip p obe w t a ve y s a p t p
is brought near the surface
to be studied.
The empty space between
the tip and the surface
represents the barrier.
Figure 9-3: Schematic view of a
scanning tunneling microscope (STM).
The tip is mounted on a piezoelectric xyz p p y
scanner. A scan of the tip over the sample
can reveal contours of the surface down
to the atomic level. An STM image is
d f i f di l d
composed of a series of scans displaced
laterally from one another.
The tip and the surface are two walls of the potential
well.
The STM allows highly
detailed images of
surfaces with resolutions
comparable to the size
of a single atom. g
An STM image of the
surface of graphite is
shown in Fig 9-4 shown in Fig.9 4.
A conductive surface is
needed.
Figure 9-4: The surface of graphite as viewed with an STM. This
type of image is capable of a lateral resolution of about 0.2 nm and a
vertical resolution of 0 001 nm
vertical resolution of 0.001 nm.
Example 9-1*
A 30-eV electron is incident on a barrier whose cross-
session is a rectangle of height 40 eV. What is the
probability that the electron will tunnel through the p ob b y e e ec o w u e oug e
barrier if its thickness is 1.0 nm? and 0.1 nm?
Solution: In this situation, U-E=40-30=10 eV=1.610
-18
J.
F E (9 2) From Eq.(9.2),
( )
(
(

~
2 4
exp
h
E U m L
T
t
(
(

=
(
18 31
10 6 . 1 10 11 . 9 2 14 . 3 4
exp
L
h
(
(

=
34
10 6 . 6
exp
When L=1 nm T~8 510
-15
If L=0 1 nm T~0 039
When L 1 nm, T~8.510 . If L 0.1 nm, T~0.039.
Topic Ten: QuantumStates of Topic Ten: Quantum States of
an Atom
In a hydrogen atom a single electron is bound to a
10.1 Hydrogen atom revisited
In a hydrogen atom, a single electron is bound to a
single proton by the attractive Coulombs force.
Atomic system can be viewed as an electron trapper in
Electron can exist only in a discrete set of quantum
t t h ith t i
y pp
which an electron is confined to a region of space.
states each with a certain energy.
Potential energy of the hydrogen atom is
Topic Ten: Quantum States of an Atom
( )
r
e
k r U
e
2
= (10.1)
h k 8 99 10
9
N
2
/C
2
i h C l b where k
e
=8.99 10
9
Nm
2
/C
2
is the Coulomb constant
and r is the radial distance between the proton and
electron.
Substitute U(r) into a 3-D Schrdinger equation and
find the appropriate solution.
Solving the equation and the energies of the allowed
states for the hydrogen atom are,
2
| |
( ) eV
6 . 13 1
2
2 2
0
2
n n a
e k
r E
e
=
|
|
.
|
\
|
=
(10.2)
n = 1, 2, 3, . . .
ll d d d h b
Allowed energy states depend on the quantum number n.
This result is exactly the same as that obtained in the
B h th Bohr theory.
For circular electron orbit, one quantum number n is
sufficient to characterize a stationary state sufficient to characterize a stationary state.
n is called the principal quantum number, an
integer, ranging from 1 to .
10.2 Quantum numbers of atomic
For a more general electronic orbit, three quantum
system
numbers are needed to define it.
They correspond to three independent degrees of freedom.
Quantum
Number
Name Allowed Values Number of
Allowed States
n
Principal quantum 1, 2, 3, . . . Any positive
number integer
l
Orbital quantum
number
0, 1, 2, . . . , n - 1 n
m
l
Orbital magnetic
quantum number
- l, - l + 1, . . . , 0, . .
. , l - 1, l
2l + 1
Any orbits that violate the above rules cannot exist.
For historical reasons all orbits having the same
For historical reasons, all orbits having the same
principal quantum number are said to form a shell.
Those orbits having the same value of n and l are said to
n Shell Symbol l Subshell symbol
g
form a subshell.
y y
1 K 0 s
2 L 1 p
3 M 2 d
4 N 3 f
5 O 4 g 5 O 4 g
6 P 5 h
. . . . . .
10 3 Spin magnetic quantumnumber
10.3 Spin magnetic quantum number
The spectra of certain gases, such as sodium vapor,
show two very closely spaced lines called a doublet show two very closely spaced lines called a doublet.
To explain this, Goudsmidt and Uhlenbeck
proposed a new quantum number m
S
, called the p p q
S
,
spin magnetic quantum number.
Convenient (but incorrect) to think of m
S
as describing
l t i i it i it bit th an electron spinning on its axis as it orbits the
nucleus.
There are only two values m
S
= , corresponding to
two directions, i,e, the electron can spin up (m
S
= )
or spin down (m
S
= -).
I t l ti In external magnetic
field, the energy of the
electrons differs slightly
for the two spin
directions. This accounts
for the doublet. for the doublet.
Electron is a point
particle, without
Figure 10-1: The spin of an electron can be
either (a) up or (b) down relative to an
spatial extent.
( ) p ( )
external magnetic field.
O h bi l i h i ( ) On each orbit, an electron can either spin up (m
S
= )
or spin down (m
S
= -).
A f b d fi d b f A quantum state of an atom must be defined by a set of
four quantum states, i.e., n, l, m
l
and m
s
.
Q H ibl ld Q. How many possible quantum states could an atom
have?
A Determined by a combination of all possible values of A. Determined by a combination of all possible values of
n, l, m
l
and m
s
.
Example 10-1*
For a hydrogen atom, determine the quantum numbers
associated with the possible states that correspond to
h i i l b the principal quantum number n=2.
n
l
m
l
m
s
subshell shell
Number of states in
subshell
1/2 1 1 2
-1/2 0 0 2
1/2 0 0 2
2s
L 2
1/2 0 1 2
-1/2 1 1 2
1/2 1 1 2
1/2 -1 1 2
-1/2 0 1 2
1/2 0 1 2
2p
L 6
-1/2 -1 1 2
10.4 The exclusion principle
p p
It turns out that n, l, m
l
, and m
s
can be used to describe
all the electronic states of an atom regardless of the all the electronic states of an atom regardless of the
number of electrons in its structure.
Q. How many electrons can have a particular set of
quantum numbers?
or
How many electrons can a particular set of
quantum numbers accommodate? qua tu u be s acco odate?
Pauli, in 1925, answered this question in the
Pauli, in 1925, answered this question in the
following statement:
No two electrons in the same atom can ever be in No two electrons in the same atom can ever be in
the same quantum state.
Therefore no two electrons can have the same set
of quantum numbers of quantum numbers.
If this principle were not valid, an atom could radiate
energy until every electron in the atom is in the lowest energy until every electron in the atom is in the lowest
possible energy state and the chemical behavior of the
elements would be grossly modified. Nature as we
know it would not exist know it would not exist.
10.5 Wolfgang Pauli (1900-1958)
g g ( )
Wolfgang Ernst Pauli (April 25,
1900 December 15, 1958) was
i h i i d f an Austrian physicist noted for
his work on the theory of spin,
and in particular the discovery of p y
the exclusion principle, which
underpins the whole of
chemistry chemistry.
In 1945, he received the Nobel Prize in Physics for his
decisive contribution through his discovery in 1925 of g y
a new law of Nature, the exclusion principle or Pauli
principle. He had been nominated for the prize by
Einstein
Einstein.
Data Source: http://en.wikipedia.org/wiki/Wolfgang_Pauli
Q. How are the quantum states for an atom filled with
l ?
electrons?
Electrons intend to fill up the state (subshell) with the
lowest energy state first lowest energy state first.
To a first approximation, energy depends only on
the principal quantum number n. It increases with
Once a subshell is filled, the next electron goes to the
t l t t b h ll
p p q
increasing n.
next lowest energy vacant subshell.
If an atom is not at its ground state (or the lowest
energy state available), it will radiate energy until it energy state available), it will radiate energy until it
reaches this state.
10.6 The periodic table
p
An orbit for an electron in an atom refers to the quantum
state of an electron characterized by the quantum
The exclusion principle suggests that there can be only
t l t i bit l ith + (|) d
y q
numbers n, l and m
l
.
two electrons in any orbital with m
s
= + (|) and m
s
=- (+).
Allowed Quantum States for an Atom having n = 3
2 1 0 1 0 0 l
3
M
2
L
1
K
n
Allowed Quantum States for an Atom having n 3.
|+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+
-2 -1 0 1 2 -1 0 1 0 -1 0 1 0 0 m
l
2
d
1
p
0
s
1
p
0
s
0
s
l
|+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ |+ m
s
2
8
18
Total=28
n = 1 K shell can only accommodate 2 electrons
n = 1 K shell can only accommodate 2 electrons.
n = 2 L shell has 2 subshells and 4 orbitals and is capable
of accepting a total of 8 electrons. p g
n = 3 M shell has 3 subshells and 9 orbitals and is
capable of accepting a total of 18 electrons.
In general, each shell can have up to 2n
2
electrons.
Hydrogen has 1 electron with the ground state
Hydrogen has 1 electron with the ground state
described by 2 sets of quantum numbers : 1, 0, 0, or
1, 0, 0, -. The electronic configuration is written as
1
1
1s
1
.
Electronic configuration: 1s
1
numbers of electrons
on the subshell
n
l
2p 2s 1s
| or +
Helium has 2 electrons with ground state quantum
numbers of 1, 0, 0, and 1, 0, 0, - . The electronic
configuration is written as 1s
2
- K shell filled.
2p 2s 1s
|+
|+
Lithium has 3 electrons with 2 in the 1s subshell and
1 in the 2s subshell (2s subshell has slightly lower
energy than 2p subshell). The electronic configuration
is written as 1s
2
2s
1
is written as 1s 2s .
2p 2s 1s
|+ | or +
Beryllium has electronic configuration of 1s
2
2s
2
.
2p 2s 1s
|+ |+
Boron has electronic configuration of 1s
2
2s
2
2p
1
. The
2p electron may be described by 6 sets of quantum
numbers corresponding to 6 states of equal energy.
2 2 1 2p 2s 1s
|+ |+
|
b h l d h l h h Carbon has 6 electrons and the 2p electrons are such that
they occupy different orbits with unpaired spins (||).
2p 2s 1s
|+ |+
| |
2p 2s 1s
|+ |+ |+
or
|+
H d R l Wh t h bit f l
Hunds Rule: When an atom has orbits of equal energy,
the order in which they are filled by electrons is such
that a maximum number of electrons have unpaired
spins.
Exceptions to the rule occur in an atom having subshells
close to being filled or half filled close to being filled or half-filled.
The Exclusion Principle can be illustrated as follows :
3
Atomic
number
K
L
3
4
5
6
Figure 10-2: The
filling of
electronic states
7
8
must obey both
the exclusion
principle and the
H d l
9
10
Hunds rule.
10
Atomic
number Z
Symbol Ground state configuration
1 H (Hydrogen) 1s
1
K
1 H (Hydrogen) 1s
1
2 He(Helium) [inert] 1s
2
3 Li (Lithium) 1s
2
2s
1
4 Be (Beryllium) 1s
2
2s
2
L
4 Be (Beryllium) 1s 2s
5 B (Boron) 1s
2
2s
2
2p
1
6 C (Carbon) 1s
2
2s
2
2p
2
7 N (Nitrogen) 1s
2
2s
2
2p
3
8 O (Oxygen) 1s
2
2s
2
2p
4
9 F (Fluorine) 1s
2
2s
2
2p
5
10 Ne (Neon) [inert] 1s
2
2s
2
2p
6
M
11 Na (Sodium) 1s
2
2s
2
2p
6
3s
1
12 Mg (Magnesium) 1s
2
2s
2
2p
6
3s
2
13 Al (Aluminum) 1s
2
2s
2
2p
6
3s
2
3p
1
14 Si (Sili ) 1
2
2
2
2
6
3
2
3
2
14 Si (Silicon) 1s
2
2s
2
2p
6
3s
2
3p
2
15 P (Phosphorus) 1s
2
2s
2
2p
6
3s
2
3p
3
16 S (Sulfur) 1s
2
2s
2
2p
6
3s
2
3p
4
17 Cl (Chlorine) 1s
2
2s
2
2p
6
3s
2
3p
5
17 Cl (Chlorine) 1s 2s 2p
6
3s 3p
5
18 Ar (Argon) [inert] 1s
2
2s
2
2p
6
3s
2
3p
6
19 K (Potassium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
20 Ca (Calcium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
K L M
M
N
( ) p p
21 Sc (Scandium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1
22 Ti (Titanium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
2
23 V (Vanadium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
3
24 Cr (Chromium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
5
25 Mn (Manganese) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
5
26 Fe (Iron) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
6
27 Co (Cobalt) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
7
28 Ni (Nickel) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
8
29 Cu (Copper) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
10
30 Z (Zi ) 1
2
2
2
2
6
3
2
3
6
4
2
3d
10
N 30 Zn (Zinc) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
31 Ga (Gallium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
1
32 Ge (Germanium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
2
33 As (Arsenic) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
3
N
33 As (Arsenic) 1s 2s 2p 3s 3p 4s 3d 4p
34 Se (Selenium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
4
35 Br (Bromine) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
5
36 Kr (Krypton) [inert] 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
O
( yp ) [ ] p p p
37 Rb (Rubidium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
1
38 Sr (Strontium) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
(4d5p6s4f5d)
s
1
s
2
p
1
p
2
p
3
p
4
p
5
s
2
p
6
K (n=1)
L ( 2) L (n=2)
M (n=3)
d
3
d
2
d
1
d
10
d
10
N (n=4)?
O (n=5)?
P (n=6)? ( )
Noble gases formed when either shell or subshell are
Elements in periodic table are arranged so that those
in a column have similar chemical properties.
Noble gases formed when either shell or subshell are
filled or there is a large gap in energy before the next
possible level is encountered.
He (helium, Z=2): 1s
2 first (K) shell filled
Ne (neon, Z=10): 1s
2
2s
2
2p
6
second (L) shell filled
( , ) p
Ar (argon, Z=18): 1s
2
2s
2
2p
6
3s
2
3p
6
p subshell in (M) shell filled
Kr (krypton Z=36):1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
p subshell in (N)
Kr (krypton, Z=36):1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
shell filled
Xe (xenon, Z=54): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
5s
2
5p
6
p subshell in (O)
shall filled
Topic Eleven: Lasers and Topic Eleven: Lasers and
Laser Light
LASER means Light Amplification for Simulated
Emission of Radiation.
Laser light is an intense, concentrated, and highly parallel
beam of coherent light.
L i h h f MASER i il d i Laser is the outgrowth of MASER, a similar device
used in microwaves instead of visible light.
In 1960 the first laser was built by T H Maiman of the In 1960, the first laser was built by T. H. Maiman of the
Hughes Aircraft Company Laboratories.
11.1 Absorption
Topic Eleven: Lasers and Laser Light
To understand the operation of a laser, we must be
familiar with the processes describing the emission and
11.1 Absorption
absorption of radiation by atoms.
Consider atomic
system with two system with two
lower states, of
energies E
1
and E
2
.
Figure 11-1: Stimulated
absorption of a photon. The
dots represent electrons. One
electron is transferred from the
ground state to the excited state
when the atom absorbs a
when the atom absorbs a
photon of energy hf = E
2
E
1
.
Stimulated absorption: when a photon of frequency f
Stimulated absorption: when a photon of frequency f
(such that the photon energy hf = E
2
- E
1
) is incident and
acting with the atom, the photon vanishes and the atomic
s stem is e cited to make the p ard transition system is excited to make the upward transition.
Excited states: atoms are raised to allowed higher
energy levels energy levels.
Excited states are metastable. Instability of the excited
states depends on the excited atoms or systems states depends on the excited atoms or systems.
11.2 Spontaneous emission
Spontaneous emission: in the instable excited states
(typically ~10
-8
s), the atom will jump back to a lower
l l d it h t i th d d energy level and emit a photon in the downward
transition process.
Figure 11-2: Spontaneous
emission of a photon by an p y
atom that is initially in the
excited state E
2
. When the
atom relaxes it to the ground
state it emits a photon of state, it emits a photon of
energy hf=E
2
E
1
.
In spontaneous emission process, a photon of energy hf
(= E
2
- E
1
) is emitted under no external influence.
Spontaneous emission happens naturally. Emitted
h d l diff f h h i photons are randomly different from each other in
propagation direction, phase angle, etc.
Phosphorescent materials glow because of a similar
process, but the excited atoms may remain in an excited
state for periods ranging from a few seconds to several
hours.
Because of this reason phosphorescent materials emit Because of this reason, phosphorescent materials emit
light after being placed in the dark.
11.3 Stimulated emission
Consider an atomic system in its excited state in the
presence of a radiation field of frequency f, such that
hf E E hf = E
2
- E
1
.
Figure 11-3: Stimulated
emission of a photon by an emission of a photon by an
incoming photon of energy hf.
Initially, the atom is in the
excited state. The incoming
photon stimulates the atom to
emit a second photon of
energy hf = E
2
E
1
.
Sti l t d i i th h t i t t ith th
Stimulated emission: the photon interacts with the
excited system to drive it downward transition to its
lower energy by emitting an additional photon.
The emitted photon is identical with the triggering or
stimulating photon - same energy, direction, phase, and
state of polarization
These two photons can cause other stimulated
emissions, leading to a chain reaction of similar
state of polarization.
g
processes - amplification.
11.4 Conditions for laser action
11.4 Conditions for laser action
1. Population inversion must be realized.
For an atomic system at thermal equilibrium, the
number of atoms occupying a state at an energy E
is determined by the exponential factor of s de e ed by e e po e a ac o o
exp(E/k
B
T), governed by the Maxwell-
Boltzmann distribution.
The ratio of the number of atoms in the upper
excited level E
2
to the number in the lower level E
1
is is
( )
( )
)
`

=
T k
E E
E n
E n
B
1 2
1
2
exp (11.1)
( )
)
T k E n
B 1
Since E
2
> E
1
, the ratio of n(E
2
)/n(E
1
) will always be
less than unity, meaning that there are fewer atoms in
the higher energy state than in the lower one in thermal the higher energy state than in the lower one in thermal
equilibrium.
5
6
7
T
Figure 11-4: The
2
3
4
k
B
T
(
E
2
-
E
1
)
/
k
B
g
Maxwell-Boltzmann
distribution.
0
1
0 0.2 0.4 0.6 0.8 1 1.2
exp(-E/k
B
T)
n(E
2
)/n(E
1
)
e
-1
=0.368 e
-3
=0.050
Example 11-1*
Estimate relative populations at room temperature (300
K) of two energy levels such that a transition from the
hi h t th l l l i i ibl di ti f higher to the lower levels gives a visible radiation of
550 nm.
Energy difference between the two levels,
10 550
10 3 10 63 . 6
9
8 34
1 2

= =

hc
E E
gy ,
From Eq.(11.1),
eV 25 . 2 J 10 6 . 3
10 550
19
= =

q ( ),
( )
( )
( )
19
2 37
23
1
3.6 10
exp exp 87 10
1.38 10 300
n E
n E
| |

= ~ ~
|

\ .
( )
1 \ .
Population inversion: there are more atoms in a higher
Population inversion: there are more atoms in a higher
energy state than in a lower state at non-thermal
equilibrium.
P i i th f ti l ti
This can be done optically by creating an intense
Pumping is the process of creating a population
inversion.
This can be done optically by creating an intense,
continuous light source around the lasing material, or
electrically by gas discharge.
2. The excited state of the system must be a metastable
state so that when population inversion is met,
stimulated emission occurs before spontaneous
emission.
3. The emitted photons must be confined in the system
p y
long enough to stimulate further emission from other
excited atoms.
Fi 11 5 S h i di f l d i Th b i h Figure 11-5: Schematic diagram of a laser design. The tube contains the atoms
that are the active medium. An external source of energy pumps the atoms
to the excited state. The parallel end mirrors confine the photons to the tube.
One mirror is made totally reflecting and the other is slightly transparent to
y g g y p
allow part of the laser beam to escape.
Spontaneous emission, stimulated emission, laser light
Key points: This illustration shows clearly
spontaneous emission, stimulated
emission, importance of an optical
resonator formed by two mirrors for
lasing, etc. lasing, etc.
11.5 Helium-neon lasers*
The three principal elements of a laser are (1) an
energy pump (2) an optical gain medium and (3) an
11.5 Helium neon lasers
energy pump, (2) an optical gain medium, and (3) an
optical resonator.
(1)Energy pump:
A 1400 V high voltage,
DC power supply
maintains a glow maintains a glow
discharge or plasma in
a glass tube containing
ti l i t an optimal mixture
(typically 5:1 to 7:1) of
helium and neon gas.
Fig re 11 6: Aphoto of a t pical HeNe laser
Figure 11-6: A photo of a typical HeNe laser.
laser
=632.8 nm
Figure 11-7: Diagram of optical and electrical components in a typical HeNe
g g p p yp
laser.
(2) Optical gain medium: To achieve laser action, it is
necessary to realize population inversion.
20.61 eV 20.66 eV
He* Ne*
632 8nm
18.70 eV
Spontaneous
Through the
collision, Ne
atoms are
excited into a
632.8nm
Figure 11-8:
Simplified atomic
energy level
diagram showing
li i
emissions deplete
the lower level to
maintain the
population
excited into a
metastable
state.
diagram showing
excited states of
atomic He and Ne
relevant to the
ti f th
Helium is
pumped
up to
excited
population
inversion.
operation of the
laser at 632.8 nm.
excited
states by
electrical
discharge
Helium Neon
(a) An energetic electron collisionally excites a He atom
to the state He* with an energy 20.61eV.
(b) The excited He* atom collides with an unexcited Ne
atom and the atoms exchange their internal energy atom and the atoms exchange their internal energy,
causing the unexcited Ne atom to be excited, i.e., Ne*
with 20.66 eV. This energy exchange process occurs
ith hi h b bilit l b f th id t l with high probability only because of the accidental near
equality of the two excitation energies of the two levels
in these atoms.
(c) The Ne* is metastable and it deexcites to a lower excited
energy level of 18.70eV by emitting a photon of
l th 6328 wavelength 6328 .
(d) The excited neon rapidly deexcites to its ground state by
emitting additional photons or by collisions with the
plasma tube walls.
(d) Because of the extreme quickness of the deexcitation (d) Because of the extreme quickness of the deexcitation
process, at any moment in the HeNe plasma, there are
more Ne atoms in Ne* state (20.66 eV) than in the
l it d t t (18 70 V) d l ti lower exited state (18.70 eV) and a population
inversion is said to be established between these two
levels.
(3) Optical resonator or cavity is formed by two highly
reflecting mirrors along the axis of the discharge. Thus,
the photons of 632 8 nm along the axis of the cavity the photons of 632.8 nm along the axis of the cavity
can be reflected hundreds of times. These reflecting
photons can interact with other excited Ne* atoms and
h i 632 8 li h i k
cause them to emit 632.8 nm light in a process known
as stimulated emission.
11.6 Laser Applications*
pp
Optical Communication
Holography
Laser cutting
Laser marking
Laser welding Laser welding
Figure 11-9: Components of
an optoelectronic an optoelectronic
communication system and
a bundle of optic febres .
Quantum Physics & Classic
Quantum theory must agree with classical theory in the
Physics
Quantum theory must agree with classical theory in the
limit in which classical theory is known to agree with
experiments.
I h d h i h l i l In other words, quantum theory must agree with classical
theory in the limit of large quantum numbers.
This is because E
n
-E
n-1
0 when n . The energy
becomes continuous, not discrete.
*For a particle in a1-D box (or infinite deep quantum p ( p q
well), the probability density becomes more uniform
when n .
For electromagnetic waves, when their hf is much For electromagnetic waves, when their hf is much
larger than k
B
T (classical measure of the mean
translation energy of a particle at temperature T), a
single photon can cause a detectable measurement
For a particle which is trapped to a small space whose
single photon can cause a detectable measurement.
Thus, the waves could show particle properties.
For a particle which is trapped to a small space whose
dimension is comparable to the particles de Broglie
wavelength, the wave character of the particle becomes
ti l d th b ti d essential and the energy becomes quantized.
Electron behaviors in nanoelectronic devices could only
be interpreted through quantum theory be interpreted through quantum theory.
Acknowledgments
I thank Professor Tjin Swee Chuan (EEE) for
hi t h l ith i th t his great help with preparing the notes.

Quantum Physics - Lecture Notes-ZQ One in One 19 Jan 2011

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Quantum Physics - Lecture Notes-ZQ One in One 19 Jan 2011

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FE1002 Ph i II FE1002 Physics II

where c is the speed of light

FE1002 Physics II Quantum Physics A/P Zhang Qing (EEE, NTU) 23

This radiation of 9.4 m is in the infrared region and

It is also in the infrared region so that most of emitted

FE1002 Physics II Quantum Physics A/P Zhang Qing (EEE, NTU) 28

Solution: They have different kinetic energies

FE1002 Physics II Quantum Physics A/P Zhang Qing (EEE, NTU) 70

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