A Day in the Life of a Nanoparticle

Or how I learned to not sunburn and still look good.

http://www.wsu.edu/~jtd/physunder/physun2.jpg
http://www.rdecom.army.mil/rdemagazine/20040
2/images/itl_arl_particles.jpg
http://media.photobucket.com/imag
e/sunscreen%20and%20nanopartic
les/vivawoman/badger-spf30-
sunscreen.jpg
Nanoparticle Uses
Sunscreens
Make-up
Automotive Paint
Sporting Goods
anti-bacterial
Hong Dong
FE-SEM: Zeiss(1550)-Clark
This image shows electrospun nylon 6 nanofibers decorated with surface bound Ag nanoparticles.
Immersing nylon 6 nanofibers into Ag colloidal solution with pH 5, Ag nanoparticles were assembled
onto nylon 6 nanofibers via interaction between nylon 6 and protection groups of Ag nanoparticles.
Future applications include antibacterial filtration.
Fiber Science and Apparel Design
Advisor Juan Hinestroza
When physicists first began investigating the structure of
atoms in the early 1900s, they uncovered a strange new
world. The subatomic particles they found -- electrons,
protons, and neutrons -- seemed to behave according to
a completely different set of laws than those governing
our everyday world.


Then, in the late 1920s, a team of young physicists led
by Niels Bohr introduced a theory that explained the
behavior of atoms and their particles. Not surprisingly,
the theory, called quantum mechanics, was as bizarre
as the world it attempted to explain.
Rather than identifying precisely where an electron should
be, for example, quantum mechanics predicts only the
probability of finding that electron in one place or another.


This description of unpredictability at the atomic level --
indeed, at any level -- was completely unacceptable to
Einstein; it flew in the face of everything he believed, and
directly contradicted his orderly theories of the universe.


Despite Einstein's disapproval, quantum mechanics has only
grown in acceptance as a theory.
The Quantum Caf
Michael Greene
http://www.pbs.org/wgbh/nova/programs/ht/qt/3012_qd_05.html
Opinions on quantum mechanics
I think it is safe to say that no
one understands quantum
mechanics. Do not keep saying
to yourself, if you can possibly
avoid it, But how can it be like
that? because you will get
down the drain into a blind
alley from which nobody has yet
escaped. Nobody knows how it
can be like that.

- Richard Feynman
Richard Feynman (1918-1988)
Those who are not shocked
when they first come across
quantum mechanics cannot
possibly have understood it.

- Niels Bohr
# How did our understanding of the atom
change in the 1920s?

# How did quantum mechanics contradict
Einstein's view of physics? What did Einstein
mean when he said, "God does not throw
dice"?

# What are some of the "bizarre" things that
quantum mechanics predicts?
Important Questions
The Birth of Modern Physics
Classical Physics of the 1890s
The Kinetic Theory of Gases
Waves and Particles
Conservation Laws and Fundamental Forces
The Atomic Theory of Matter
Outstanding Problems of 1895 and New
Horizons
The more important fundamental laws and facts of physical science have all
been discovered, and these are now so firmly established that the possibility
of their ever being supplanted in consequence of new discoveries is
exceedingly remote Our future discoveries must be looked for in the sixth
place of decimals. - Albert A. Michelson, 1894

There is nothing new to be discovered in physics now. All that remains is more
and more precise measurement. - Lord Kelvin, 1900
James Clerk Maxwell
Classical Physics of the 1890s
Mechanics
Thermodynamics
Electromagnetism
0 0
E
B
t
c
c
c
V =
B
E
t
c
c
V=
0 B V =
0
/ E q c V =
Electromagnetism culminated
with Maxwells Equations
Gaussslaw:
(electric field)


Gaussslaw:
(magnetic field)


Faradayslaw:



Ampres law:

James Clerk Maxwell
(1831-1879)
in the presence of
only stationary
charges.
Faraday saw the World in a new way!
The Nature of Light
Newton promoted the corpuscular
(particle) theory

Particles of light travel in straight lines
or rays
Explained sharp shadows
Explained reflection and refraction
"I procured me a triangular glass prism to try
therewith the celebrated phenomena of
colours." (Newton, 1665)
Newton in action
The Nature of Light
Huygens promoted the wave theory.
He explained polarization,
reflection, refraction, and double
refraction.
Double refraction
Christiaan Huygens
(1629-1695)
He realized that light propagates as a
wave from the point of origin.
He realized that light slowed down on
entering dense media.
Diffraction confirmed light to be a wave.
Diffraction patterns
One slit


Two slits
WhilescientistsofNewtonstimethought
shadowsweresharp,Youngstwo-slit
experiment could only be explained by
light behaving as a wave. Fresnel
developed an accurate theory of diffraction
in the early 19
th
century.
Augustin Fresnel
Waves can interfere.
Maxwell strove to prove his Mentor correct
Light waves were found to be solutions to
Maxwells Equations.
All electromagnetic waves
travel in a vacuum with
a speed c given by:
infrared X-ray UV v
i
s
i
b
l
e

wavelength (nm)
microwave
radio
10
5
10
6
gamma-ray
The electromagnetic spectrum is vast.
where
0
and
0
are the permeability and permittivity of free space
Light is an electromagnetic wave.
The electric (E) and magnetic (B) fields are in phase.
The electric field, the magnetic field, and the propagation direction are
all perpendicular.
Triumph of Classical Physics:
The Conservation Laws
Conservation of energy: The sum of energy
(in all its forms) is conserved (does not
change) in all interactions.

Conservation of linear momentum: In the
absence of external forces, linear
momentum is conserved in all interactions.

Conservation of angular momentum: In the
absence of external torque, angular
momentum is conserved in all interactions.

Conservation of charge: Electric charge is
conserved in all interactions.
These laws remain
the key to interpreting
even particle physics
experiments today.
Problems in 19
th
-century physics
In a speech to the Royal Institution in 1900, Lord Kelvin himself
describedtwodarkcloudsonthehorizonofphysics:
The question of the existence
of an electro-magnetic
mediumreferred to as
etheroraether.

The failure of classical
physics to explain blackbody
radiation.
The Ultraviolet Catastrophe
Lord Rayleigh used the classical theories of electromagnetism
and thermodynamics to show that the blackbody spectrum
should be:
This worked at longer wavelengths but deviates badly at short ones.
This problem became known as the ultraviolet catastrophe and was one of
themanyeffectsclassicalphysicscouldntexplain.
Rayleigh-Jeans Formula
More problems: discrete spectral lines
Wavelength
Emissio
n
spectra
from
gases of
hot
atoms.
For reasons then unknown, atomic gases emitted only certain narrow
frequencies, unique to each atomic species.
Additional discoveries in 1895-7 contributed to the
complications.
X-rays (Roentgen)

Radioactivity (Becquerel)

Electron (Thomson)

Zeeman effect
Roentgensx-ray
imageofhiswifeshand
(with her wedding ring)
The Beginnings of Modern Physics
These new discoveries and the
many resulting complications
required a massive revision of
fundamental physical
assumptions.

The introduction (~1900) of the
modern theories of special
relativity and quantum
mechanics became the
starting point of this most
fascinating revision. General
relativity (~1915) continued it.
Log
(size)
S
p
e
e
d

0
c
19
th
-
century
physics
G
e
n
e
r
a
l

r
e
l
a
t
i
v
i
t
y

Q
u
a
n
t
u
m

m
e
c
h
a
n
i
c
s

Special
relativity
Triumph of Classical Physics:
The Conservation Laws
Conservation of energy: The sum of energy
(in all its forms) is conserved (does not
change) in all interactions.

Conservation of linear momentum: In the
absence of external forces, linear
momentum is conserved in all interactions.

Conservation of angular momentum: In the
absence of external torque, angular
momentum is conserved in all interactions.

Conservation of charge: Electric charge is
conserved in all interactions.
These laws remain
the key to interpreting
even particle physics
experiments today.
For our sunscreen to work we will need to look
at an experiment designed to determine how
tightly bound electrons are to a surface.
This requires coming up with Planck's Constant.

This also requires the determination of the work Function.
Work function experiment.
http://www.walter-fendt.de/ph11e/photoeffect.htm
Workfunction for ZnO is ~4.5
What is Quantum Physics?
Quantum physics is a branch of Science
that deals with discrete, indivisible units of
energy called quanta as described by
Quantum Theory.
There are five main ideas represented in
Quantum Theory which are:
1. Energy is not continuous, but comes in
small, but discrete units.
2. The elementary particles behave both
like particles and like waves.
3. The movement of these particles is
inherently random.
4. It is physically impossible to know both
the position and momentum of a particle at
any instant in time so that the more accurate
the measurement of one is, the more
inaccurate the measure of the other is.
5. The atomic world is NOTHING like the
world we live in.
The Atomic Models of Thomson and
Rutherford
Rutherford Scattering
The Classic Atomic Model
The Bohr Model of the Hydrogen Atom
Successes & Failures of the Bohr Model
Characteristic X-Ray Spectra and Atomic
Number
Atomic Excitation by Electrons
Structure of the Atom
The opposite of a correct statement is a false statement. But the opposite of a
profound truth may well be another profound truth.
An expert is a person who has made all the mistakes that can be made in a very
narrow field.
Never express yourself more clearly than you are able to think.
Prediction is very difficult, especially about the future.
- Niels Bohr
Niels Bohr (1885-1962)
Structure of the Atom
Evidence in 1900 indicated that
the atom was not a fundamental unit:
1) There seemed to be too many kinds
of atoms, each belonging to a distinct chemical
element (way more than earth, air, water, and fire!).
2) Atoms and electromagnetic phenomena were intimately
related (magnetic materials; insulators vs. conductors;
different emission spectra).
3) Elements combine with some elements but not with others,
a characteristic that hinted at an internal atomic structure
(valence).
4) The discoveries of radioactivity, x rays, and the electron (all
seemed to involve atoms breaking apart in some way).
Knowledge of atoms in 1900
Electrons (discovered in
1897) carried the negative
charge.
Electrons were very light,
even compared to the atom.
Protons had not yet been
discovered, but clearly
positive charge had to be
present to achieve charge
neutrality.
InThomsonsview,whentheatomwasheated,theelectronscould
vibrate about their equilibrium positions, thus producing
electromagnetic radiation.
Unfortunately,Thomsoncouldntexplainspectrawiththismodel.
Thomsons
Atomic Model
Thomsonsplum-pudding
model of the atom had the
positive charges spread
uniformly throughout a
sphere the size of the atom,
with electrons embedded in
the uniform background.

Experiments of Rutherford, Geiger and
Marsden
Rutherford, Geiger, and Marsden
conceived a new technique for
investigating the structure of
matter by scattering o particles
from atoms.
Experiments of Rutherford, Geiger and
Marsden 2
Geiger showed that many o particles were scattered from thin
gold-leaf targets at backward angles greater than 90.
Experimental results
were not consistent with
Thomsonsatomicmodel.
Rutherford proposed that
an atom has a positively
charged core (nucleus)
surrounded by the
negative electrons.
Geiger and Marsden
confirmed the idea in
1913.
Rutherfords Atomic Model
Ernest Rutherford
(1871-1937)
2 2
2
0
1 v
4
e
e m
F
r r tc
= =
The Classical Atomic Model
Consider an atom as a planetary system.
TheNewtons2
nd
Law force of attraction on
the electron by the nucleus is:
where v is the tangential velocity of the
electron:
The total energy is then:
0
v
4
e
mr tc
=
2
2
1 1
2 2
0
v
4
e
K m
r tc
= =
This is negative, so
the system is bound,
which is good.
The Planetary Model is Doomed
From classical E&M theory, an accelerated electric charge radiates
energy (electromagnetic radiation), which means the total energy
must decrease. So the radius r must decrease!!
Physics had reached a turning point in 1900 withPlancks
hypothesis of the quantum behavior of radiation, so a radical
solution would be considered possible.
Electron
crashes
into the
nucleus!?
The Bohr Model of the Hydrogen Atom
Bohrsgeneralassumptions:
1. Stationary states, in which orbiting
electrons do not radiate energy, exist in
atoms and have well-defined energies,
E
n
. Transitions can occur between them,
yielding light of energy:
E = E
n
E
n
= hv
2. Classical laws of physics do not apply
to transitions between stationary states,
but they do apply elsewhere.
3. The angular momentum of the n
th
state is:
where n is called the Principal Quantum Number.
n
n = 1
n = 3
n = 2
Angular
momentum is
quantized!
Consequences of the Bohr Model
The angular momentum is:
n r m L = = v
0
v
4
e
mr tc
=
mr n / v =
0
4
2 2 2
2 2
n e
m r mr tc
=
But: So:
Solving for r
n
:
2
0 n
r n a =
So the velocity is:
0
0
4
2
2
a
me
tc

where:
a
0
is called the Bohr radius. Its the diameter of the Hydrogen
atom (in its lowest-energy, or ground, state).
a
0

Bohr Radius
The Bohr radius,




is the radius of the unexcited hydrogen atom and is equal to:




ThegroundstateHydrogenatomdiameteris:
0
0
4
2
2
a
me
tc

/
The Hydrogen
Atom Energies
So the energies of the stationary
states are:
where E
0
= 13.6 eV.
r
e
E
0
2
8tc

=
0
4
2 2
n
2
n
r
me
tc
=
Use the classical
result for the
energy:

and:
E
n
= E
0
/n
2
or:
The Hydrogen Atom
Emission of light occurs when the atom is in an excited state
and decays to a lower energy state (n
u
n

).
u
h E E v =
1 h
c hc
v v

= = =
R

is the Rydberg constant.

where v is the frequency of a photon.
3
0
(4 )
4
2
me
R
c t c

Transitions
in the
Hydrogen
Atom
The atom will remain
in the excited state
for a short time
before emitting a
photon and returning
to a lower stationary
state. In equilibrium,
all hydrogen atoms
exist in n = 1.
Shells have letter names:
K shell for n = 1
L shell for n = 2


The atom is most stable in its
ground state.



When it occurs in a heavy atom, the radiation emitted is an x-ray.
It has the energy E (x-ray) = E
u
E

.
Characteristic X-Ray
Spectra and Atomic
Number
An electron from higher
shells will fill the inner-shell vacancy at lower energy.
The Correspondence
Principle
In the limits where classical and
quantum theories should agree,
the quantum theory must reduce
the classical result.
Bohrscorrespondenceprinciple
is rather obvious:
Successes and Failures of the Bohr
Model
The electron and
hydrogen nucleus
actually revolve
about their mutual
center of mass.
The electron mass is replaced
by its reduced mass:


The Rydberg constant for infinite nuclear mass, R

, is replaced by R.
Success:
Limitations of the
Bohr Model
Works only for single-electron(hydrogenic)atoms.

Could not account for the intensities or the fine structure of
the spectral lines (for example, in magnetic fields).

Could not explain the binding of atoms into molecules.
Failures:
The Bohr model was a great
step in the new quantum
theory, but it had its limitations.