EARLY QUANTUM THEORY

MODELS OF THE ATOM

DR MARTA STASIAK
DEPARTMENT OF CYTOBIOLOGY AND PROTEOMICS

lecture based on © 2016 Pearson Education, Ltd.

 Early Quantum Theory and
Models of the Atom

© 2016 Pearson Education,

Ltd.
 CONTENTS
• Discovery and Properties of the Electron
• Blackbody Radiation; Planck’s Quantum Hypothesis
• Photon Theory of Light and the Photoelectric Effect
• Energy, Mass, and Momentum of a Photon
• Compton Effect
• Photon Interactions; Pair Production
• Wave-Particle Duality; the Principle of Complementarity
• Wave Nature of Matter
• Electron Microscopes
• Early Models of the Atom
• Atomic Spectra: Key to the Structure of the Atom
• The Bohr Model
• de Broglie’s Hypothesis Applied to Atoms
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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
In the late 19th century, discharge tubes were made that emitted
“cathode rays.”

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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
It was found that these rays could be deflected by electric or
magnetic fields.

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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
By accelerating the rays through a known potential and then
measuring the radius of their path in a known magnetic field, the
charge to mass ratio could be measured:

The result is e/m = 1.76 × 1011 C/kg.

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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
Cathode rays were soon called electrons.
Millikan devised an experiment to measure the charge on the
electron by measuring the electric field needed to suspend an oil
droplet of known mass between parallel plates.

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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
The mass and charge of each droplet were measured;
careful analysis of the data showed that the charge was always an
integral multiple of a smallest charge, e.

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 DISCOVERY AND PROPERTIES OF THE
ELECTRON
The currently accepted value of e is:
e = 1.602 × 10−19 C

Knowing e allows the electron mass to be calculated:

me = 9.11 × 10−31 kg

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 BLACKBODY RADIATION
All objects emit radiation whose total intensity is proportional
to the fourth power of their temperature.
This is called thermal radiation;
A blackbody is an object that emits thermal radiation only.
The spectrum of blackbody radiation has been measured; it is
found that the frequency of peak intensity increases linearly
with temperature.

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 BLACKBODY RADIATION
This figure shows
blackbody radiation curves
for three different
temperatures. Note that
frequency increases to
the left.

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 BLACKBODY RADIATION;
PLANCK’S QUANTUM HYPOTHESIS
This spectrum could not be reproduced using 19th-century physics.
A solution was proposed by Max Planck in 1900:
The energy of atomic oscillations within atoms cannot have an
arbitrary value; it is related to the frequency:
E = hf

The constant h is now called Planck’s constant.

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 PLANCK’S QUANTUM HYPOTHESIS
Planck found the value of his constant by fitting blackbody curves:
h = 6.626 × 10−34 J⋅s

Planck’s proposal was that the energy of an oscillation had to be

an integral multiple of hf.
This is called the quantization of energy.

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 ENERGY, MASS, AND MOMENTUM OF A
PHOTON
Photons must travel at the speed of light.
Looking at the relativistic equation for momentum, it is clear that
this can only happen if its rest mass is zero.
We already know that the energy is hf; we can put this in the
relativistic energy-momentum relation and find the momentum:

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
Einstein suggested that, given the success of Planck’s theory,
light must exist as a set of small energy packets:

These tiny packets, or particles, are called photons.

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
The photoelectric effect:
If light strikes a metal, electrons
are emitted. The effect does not
occur if the frequency of the
light is too low; the kinetic
energy of the electrons
increases with frequency.

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
If light is a wave, theory predicts for the photoelectric effect:
1. Number of electrons and their energy should increase with
intensity
2. Frequency should not matter

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
If light is particles (photons), theory predicts for the photoelectric
effect:
• Increasing intensity increases number of electrons but not energy
• Above a minimum energy required to break atomic bond, kinetic
energy will increase linearly with frequency
• There is a cutoff frequency below which no electrons will be
emitted, regardless of intensity

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
The particle theory assumes that an electron absorbs a single photon.
Plotting the kinetic energy vs. frequency:
This shows clear agreement with the photon theory, and not with wave
theory.

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 PHOTON THEORY OF LIGHT
AND THE PHOTOELECTRIC EFFECT
The photoelectric effect is how “electric eye” detectors work. It
is also used for movie film soundtracks.

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 COMPTON EFFECT
Compton did experiments in which he scattered X-rays from
different materials.
He found that the scattered X-
rays had a slightly longer
wavelength than the incident
ones, and that the wavelength
depended on the scattering
angle:

This is another effect that is correctly predicted by the photon model and
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 PAIR PRODUCTION

In pair production, energy, electric charge, and momentum must

all be conserved.
Energy will be conserved
through the mass and
kinetic energy of the
electron and positron;
their opposite charges
conserve charge; and the
interaction must take
place in the electro-
magnetic field of a
nucleus, which can
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 PHOTON INTERACTIONS

Photons passing through matter can undergo the following

interactions:
1. Photoelectric effect: photon is completely absorbed,
electron is ejected
2. Photon may be totally absorbed by electron, but not
have enough energy to eject it; the electron moves into
an excited state
3. Compton Effect: the photon can scatter from an atom
and lose some energy
4. The photon can produce an electron-positron pair.
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 WAVE-PARTICLE DUALITY;
THE PRINCIPLE OF COMPLEMENTARITY
We have phenomena such as diffraction and interference that
show that light is a wave, and phenomena such as the
photoelectric effect and the Compton effect that show that it is a
particle.
Which is it?
This question has no answer; we must accept the dual wave-
particle nature of light.

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 WAVE-PARTICLE DUALITY;
THE PRINCIPLE OF COMPLEMENTARITY
The principle of complementarity states that both the wave and
particle aspects of light are fundamental to its nature.
Indeed, waves and particles are just our interpretations of how
light behaves.

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 WAVE NATURE OF MATTER
Just as light sometimes behaves as a particle, matter sometimes
behaves like a wave.
The wavelength of a particle of matter is:

This wavelength is extraordinarily small for most objects. The

wave nature of matter becomes more important for very light
particles such as the electron.

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 WAVE NATURE OF MATTER
Electron wavelengths can
easily be on the order of
10−10 m; electrons can be
diffracted by crystals just
as X-rays can.

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 ELECTRON MICROSCOPES
The wavelength of electrons will vary with energy, but is still quite
short. This makes electrons useful for imaging—remember that the
smallest object that can be resolved is about one wavelength.
Electrons used in electron microscopes have wavelengths of about
0.004 nm.

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 ELECTRON MICROSCOPES
Transmission electron
microscope—the electrons are
focused by magnetic coils

Staphylococcus aureus platinum replica image

shot on a TEM at 50,000x magnification
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 ELECTRON MICROSCOPES
Scanning electron
microscope—the electron
beam is scanned back and
forth across the object to be
imaged

Image of pollen grains taken on an SEM shows the

characteristic depth of field of SEM micrographs
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 ELECTRON MICROSCOPES
Scanning tunneling microscope—up and down motion of the
probe keeps the current constant.
Plotting that motion
produces an image of
the surface.

An STM image of a single-walled carbon nanotube

https://en.wikipedia.org/wiki/Scanning_tunneling_microscope
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 EARLY MODELS OF THE ATOM
It was known in the late 19th century that atoms were electrically
neutral, but that they could become charged, implying that there
were positive and negative charges and that some of them could
be removed.

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 EARLY MODELS OF THE ATOM
One popular atomic model was the “plum-pudding” model. This
model had the atom
consisting of a bulk positive
charge, with negative
electrons buried throughout.

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 EARLY MODELS OF THE ATOM
Around 1911, Rutherford did an experiment that showed that the
positively charged nucleus must be extremely small compared
to the rest of the atom. He scattered alpha particles—helium
nuclei—from a metal foil and observed the scattering angle. He
found that some of the angles were far larger than the plum-
pudding model would allow.

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 EARLY MODELS OF THE ATOM
The only way to account for the large angles was to assume that all
the positive charge was contained within a tiny volume.

Now we know that the radius of the nucleus is 1/10000 that of the
atom.
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 EARLY MODELS OF THE ATOM
Therefore, Rutherford’s model of the atom is mostly empty space:

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 ATOMIC SPECTRA:
KEY TO THE STRUCTURE OF THE ATOM
A very thin gas heated in a discharge tube emits light only at
characteristic frequencies.

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 ATOMIC SPECTRA:
KEY TO THE STRUCTURE OF THE ATOM
An atomic spectrum is a line spectrum—only certain frequencies
appear. If white light passes through such a gas, it absorbs at those
same frequencies.

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 ATOMIC SPECTRA:
KEY TO THE STRUCTURE OF THE ATOM
The wavelengths of electrons emitted from hydrogen have a
regular pattern:

This is called the Balmer series. R is the Rydberg constant:

R = 1.0974 × 107 m−1

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 ATOMIC SPECTRA:
KEY TO THE STRUCTURE OF THE ATOM
Other series include the Lyman series:

And the Paschen series:

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 ATOMIC SPECTRA:
KEY TO THE STRUCTURE OF THE ATOM
A portion of the complete spectrum of hydrogen is shown here.
The lines cannot be explained by the Rutherford theory.

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 THE BOHR ATOM
Bohr proposed that the possible energy states for atomic
electrons were quantized—only certain values were possible.
Then the spectrum could be explained as transitions from one
level to another.

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 THE BOHR ATOM
Bohr found that the angular momentum was quantized:

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 THE BOHR ATOM
An electron is held in orbit by the Coulomb force:

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 THE BOHR ATOM
Using the Coulomb force, we can calculate the radii of the orbits:

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 THE BOHR ATOM

The lowest energy

level is called the
ground state;
the others are excited
states.

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 THE BOHR ATOM
The correspondence principle applies here as well—when the
differences between quantum levels are small compared to
the energies, they should be imperceptible.

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 DE BROGLIE’S HYPOTHESIS APPLIED
TO ATOMS
De Broglie’s hypothesis is the one associating a wavelength with
the momentum of a particle. He proposed that only those orbits
where the wave would be a circular standing wave will occur.
This yields the same relation that Bohr had proposed.
In addition, it makes more reasonable the fact that the electrons
do not radiate, as one would otherwise expect from an
accelerating charge.

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 DE BROGLIE’S HYPOTHESIS APPLIED
TO ATOMS
These are circular standing
waves for n = 2, 3, and 5.

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 SUMMARY
• Planck’s hypothesis: molecular oscillation energies are
quantized

• Light can be considered to consist of photons, each of energy

• Photoelectric effect: incident photons knock electrons out of

material

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 SUMMARY
• Compton effect and pair production also support photon theory
• Wave-particle duality—both light and matter have both wave
and particle properties
• Wavelength of an object with mass:

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 SUMMARY
• Principle of complementarity: both wave and particle
properties are necessary for complete understanding
• Rutherford showed that atom has tiny nucleus
• Line spectra are explained by electrons having only certain
specific orbits
• Ground state has the lowest energy; the others are called
excited states

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QUANTUM MECHANICS OF
ATOMS
DR MARTA STASIAK
DEPARTMENT OF CYTOBIOLOGY AND PROTEOMICS

lecture based on © 2016 Pearson Education, Ltd.

 Quantum Mechanics of Atoms

© 2016 Pearson
Education, Ltd.
 CONTENTS
• Quantum Mechanics—A New Theory
• The Wave Function and Its Interpretation;
the Double-Slit Experiment
• The Heisenberg Uncertainty Principle
• Philosophic Implications; Probability versus Determinism
• Quantum-Mechanical View of Atoms
• Quantum Mechanics of the Hydrogen Atom;
Quantum Numbers
• Multielectron Atoms; the Exclusion Principle
• The Periodic Table of Elements
• X-Ray Spectra and Atomic Number
• Fluorescence and Phosphorescence
• Lasers
• Holography
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QUANTUM MECHANICS—A NEW THEORY

Quantum mechanics incorporates wave-particle duality, and

successfully explains energy states in complex atoms and
molecules, the relative brightness of spectral lines, and many
other phenomena.
It is widely accepted as being the fundamental theory underlying
all physical processes.
Quantum mechanics is essential to understanding atoms and
molecules, but can also have effects on larger scales.

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 THE WAVE FUNCTION AND ITS
INTERPRETATION;
THE DOUBLE-SLIT EXPERIMENT
An electromagnetic wave has oscillating electric and magnetic
fields. What is oscillating in a matter wave?
This role is played by the wave function, Ψ. The square of the
wave function at any point is proportional to the number of
electrons expected to be found there.
For a single electron, the wave function is the probability of
finding the electron at that point.

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 THE WAVE FUNCTION AND ITS
INTERPRETATION;
THE DOUBLE-SLIT EXPERIMENT
For example: the interference pattern is observed after many
electrons have gone through the slits.
If we send the
electrons through one
at a time, we cannot
predict the path any
single electron will
take, but we can
predict the overall
distribution.

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 THE HEISENBERG UNCERTAINTY
PRINCIPLE
Quantum mechanics tells us there are limits to measurement—
not because of the limits of our instruments, but inherently.
This is due to the wave-particle duality, and to interaction
between the observing equipment and the object being
observed.

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 THE HEISENBERG UNCERTAINTY
PRINCIPLE
Imagine trying to see an electron
with a powerful microscope. At
least one photon must scatter off
the electron and enter the
microscope, but in doing so it will
transfer some of its momentum to
the electron.

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 THE HEISENBERG UNCERTAINTY
PRINCIPLE
The uncertainty in the momentum of the electron is taken to be
the momentum of the photon—it could transfer anywhere from
none to all of its momentum.
In addition, the position can only be measured to about one
wavelength of the photon.

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 THE HEISENBERG UNCERTAINTY
PRINCIPLE
Combining, we find the combination of uncertainties:

This is called the Heisenberg uncertainty principle.

It tells us that:
the position and momentum cannot simultaneously be measured
with precision.

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 THE HEISENBERG UNCERTAINTY
PRINCIPLE
This relation can also be written as a relation between the
uncertainty in time and the uncertainty in energy:

This says that if an energy state only lasts for a limited time, its
energy will be uncertain. It also says that conservation of energy
can be violated if the time is
short enough.

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 PHILOSOPHIC IMPLICATIONS;
PROBABILITY VERSUS DETERMINISM
The world of Newtonian mechanics is a deterministic one. If
you know the forces on an object and its initial velocity, you can
predict where it will go.
Quantum mechanics is very different—you can predict what
masses of electrons will do, but have no idea what any
individual one will.

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QUANTUM-MECHANICAL VIEW OF ATOMS

Since we cannot say exactly where an electron is, the Bohr

picture of the atom, with electrons in neat orbits, cannot be
correct.
Quantum theory describes
an electron probability
distribution; this figure
shows the distribution
for the ground state of
hydrogen.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
There are four different quantum numbers needed to specify the
state of an electron in an atom.
1. Principal quantum number n gives the total energy:

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
2. Orbital quantum number l gives the angular momentum;
l can take on integer values from 0 to n − 1.

3. The magnetic quantum number, ml, gives the direction of

the electron’s angular momentum, and can take on integer
values from −l to +l.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
This plot indicates the
quantization of angular
momentum direction for
l = 2. The other two
components of the angular
momentum are undefined.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
4. The spin quantum number, ms, which for an electron can
take on the values +½ and −½. The need for this quantum
number was found by experiment; spin is an intrinsically
quantum mechanical quantity, although it mathematically
behaves as a form of angular momentum.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
This table summarizes the four quantum numbers.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
The angular momentum quantum numbers do not affect the
energy level much, but they do change the spatial distribution
of the electron cloud.

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 QUANTUM MECHANICS OF THE
HYDROGEN ATOM; QUANTUM NUMBERS
“Allowed” transitions between energy levels occur between
states whose value of l differ by one:

Other, “forbidden,” transitions also occur but with much lower

probability.

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 MULTIELECTRON ATOMS;
THE EXCLUSION PRINCIPLE
Complex atoms contain more than one electron, so the interaction
between electrons must be accounted for in the energy levels.
This means that the energy depends on both n and l.
A neutral atom has Z electrons, as well as Z protons in its
nucleus. Z is called the atomic number.

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 MULTIELECTRON ATOMS;
THE EXCLUSION PRINCIPLE
In order to understand the electron distributions in atoms, another
principle is needed. This is the Pauli exclusion principle:
No two electrons in an atom can occupy the same quantum state.
The quantum state is specified by the four quantum numbers; no
two electrons in the same atom can have the same set.

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 MULTIELECTRON ATOMS;
THE EXCLUSION PRINCIPLE
This chart shows the occupied—and some unoccupied—states
in He, Li, and Na.

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 PERIODIC TABLE OF THE ELEMENTS
We can now understand the organization of the periodic table.
Electrons with the same n are in the same shell. Electrons with
the same n and l are in the same subshell.
The exclusion principle limits the maximum number of
electrons in each subshell to 2(2l + 1).
https://www.khanacademy.
org/science/chemistry/elec
tronic-structure-of-
atoms/electron-
configurations-jay-
sal/v/orbitals

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 THE PERIODIC TABLE OF THE ELEMENTS

Each value of l is given its

own letter symbol.

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 THE PERIODIC TABLE OF THE ELEMENTS

Electron configurations are written by giving the value for n,

the letter code for l, and the number of electrons in the subshell
as a superscript.
For example, here is the ground-state configuration of sodium:
1s22s22p63s1

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 THE PERIODIC TABLE OF THE ELEMENTS

This table shows the

configuration of the
outer electrons only.

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 THE PERIODIC TABLE OF THE ELEMENTS

Atoms with the same number of electrons in their outer shells

have similar chemical behavior. They appear in the same
column of the periodic table.
The outer columns—those with full, almost full, or almost empty
outer shells—are the most distinctive.
The inner columns, with partly filled shells, have more similar
chemical properties.

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 X-RAY SPECTRA AND ATOMIC NUMBER

The effective charge that an electron “sees” is the charge on the

nucleus shielded by inner electrons. Only the electrons in the first
level see the entire nuclear charge.

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 X-RAY SPECTRA AND ATOMIC NUMBER

The energy of a level is proportional to Z 2 , so the wavelengths

corresponding to transitions to the n = 1 state in high-Z atoms are
in the X-ray range.

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 X-RAY SPECTRA AND ATOMIC NUMBER

Inner electrons can be ejected by high-energy electrons. The

resulting X-ray spectrum is characteristic of the element.
This example is for
molybdenum.

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 X-RAY SPECTRA AND ATOMIC NUMBER

Measurement of these spectra allows determination of inner

energy levels, as well as Z, as the wavelength of the shortest X-
rays is inversely proportional to Z 2 .

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 X-RAY SPECTRA AND ATOMIC NUMBER

The continuous part of the X-

ray spectrum comes from
electrons that are decelerated
by interactions within the
material, and therefore emit
photons.
This radiation is called:
bremsstrahlung
(“braking radiation”).

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FLUORESCENCE AND PHOSPHORESCENCE

If an electron is excited to a higher energy state, it may emit

two or more photons of longer wavelength as it returns to the
lower level.

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FLUORESCENCE AND PHOSPHORESCENCE

Fluorescence occurs when the absorbed photon is ultraviolet

and the emitted photons are in the visible range.
Phosphorescence occurs when the electron is excited to a
metastable state; it can take seconds or more to return to the
lower state. Meanwhile, the material glows.

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 LASERS
A laser produces a narrow, intense beam of coherent light. This
coherence means that, at a given cross section, all parts of the
beam have the same phase.
The top figure shows absorption of a
photon. The bottom picture shows
stimulated emission—if the atom is
already in the excited state, the
presence of another photon of the
same frequency can stimulate the
atom to make the transition to the
lower state sooner. These photons are
in phase.

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 LASERS
To obtain coherent light from stimulated emission, two
conditions must be met:
1. Most of the atoms must be in the excited state; this is called
an inverted population.

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 LASERS
2. The higher state must be a metastable state, so that once the
population is inverted, it stays that way. This means that
transitions occur through stimulated emission rather than
spontaneously.

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 LASERS
The laser beam is narrow, only spreading due to diffraction,
which is determined by the size of the end mirror.
An inverted population can
be created by exciting
electrons to a state from
which they decay to a
metastable state. This is
called optical pumping.

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 LASERS
A metastable state can also be created through interactions
between two sets of atoms, such as in a helium-neon laser.

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 LASERS
Lasers are used for a wide variety of applications: surgery,
machining, surveying, reading bar codes, CDs, and DVDs, and so
on. This diagram shows how a CD is read.

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 HOLOGRAPHY
Holograms are created using the coherent light of a laser. The
beam is split, allowing the film to record both the intensity and
the relative phase of the light. The resulting image, when
illuminated by a laser, is three-dimensional.
White-light holograms are made with a laser but can be viewed in
ordinary light. The emulsion is thick, and contains interference
patterns that make the image somewhat three-dimensional.

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 SUMMARY
• Quantum mechanics is the basic theory at the atomic level; it is
statistical rather than deterministic
• Heisenberg uncertainty principle:

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 SUMMARY
• Electron state in atom is specified by four numbers, n, l, ml,
and ms
• n, the principal quantum number, can have any integer value,
and gives the energy of the level
• l, the orbital quantum number, can have values from 0 to n − 1
• ml, the magnetic quantum number, can have values from −l to
+l
• ms, the spin quantum number, can be +½ or −½

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 SUMMARY
• Energy levels depend on n and l, except in hydrogen. The other
quantum numbers also result in small energy differences.
• Pauli exclusion principle: no two electrons in the same atom
can be in the same quantum state
• Electrons are grouped into shells and subshells
• Periodic table reflects shell structure
• X-ray spectrum can give information about inner levels and Z
of high-Z atoms

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