CHAPTER 4

Structure of the Atom / Particle nature of matter

4.0 Elements and Atoms throughout the ages

4.1 The plum pudding / raisin cake atom model of J.J. Thomson
4.2 Rutherford Scattering / Planetary model of the atom?
4.3 The instability of the classic “solar system” model of atoms
3.3 Line spectra of elements, Balmer’s numerology and Rydberg’s equation and
constant
4.4 The Bohr Model of the Hydrogen Atom; Sommerfeld - fine structure constant
4.5.1 Successes
4.5.2 Failures
4.6 Shell structure of atoms, characteristic X-Ray Spectra, Moseley’s fit and it’s
support of Bohr’s model
4.7. There are also Auger electrons, not only characteristic X-rays
4.8. quantum jumps in physics and how the general public misunderstands the
concept

In the present first part of the paper the mechanism of the binding of
electrons by a positive nucleus is discussed in relation to Planck’s theory.
It will be shown that it is possible from the point of view taken to account in
a simple way for the law of the line spectrum of hydrogen. - Niels Bohr, 1
1913
Various Greek (and Indian) philosophers had only a few elements, concept of
an atom that is indivisible smallest unit of any form of matter

Various atoms and molecules as depicted

in John Dalton's ”A New System of
Chemical Philosophy” (1808).

Law of constant proportion in chemical

reactions, atoms must exist for chemical
book keeping reasons

2H2 + O2 -> 2H2O

2
Faraday, 1838:
Atoms have
“electrical
constituents”

3
John Joseph Thomson, 1897

Electrons are negatively charged particles that can be “pulled out” of any metal by
a strong electric field (the “thingies” pulled out are all identical and have a charge
to mass ratio about 2,000 times larger than hydrogen ions (which we now know to
be protons)

So atoms cannot be indivisible, if not

Previous indivisible, they must have some internal
chapter structure that is responsible for the
physical and chemical properties of the
atoms of the various elements
4
There is also radioactivity (from 1896 onwards):
electrons and other particles, e.g. alpha
particles, (we now know nuclei of He, two
protons + two neutrons) come out of the atoms
of certain radioactive elements

end of the second part of this course, nuclear

physics

5
 Einstein’s PhD thesis and the related 1905 also start of quantitative
paper, atoms must exist for physical reasons nanoscience

A. Einstein, “Eine neue

Bestimmung der
Moleküldimensionen”, Annalen der
Physik, vol. 19, pp. 289-306, 1906

ibid vol. 34, pp. 591-

592, 1911

6
Big questions: What is the true nature of atoms?
What is their internal structure that is responsible for the
chemical and physical properties of the atoms of the various
chemical elements, expanded to molecules and condensed
matter

Smaller questions (the answers to which will help with the big
questions above:
How come there are characteristic emission and absorption spectra for all
of the elements?
How come there are characteristic X-ray emission spectra for the
elements (there are of course also characteristic X-ray absorption spectra
– not part of this course, there are also characteristic γ-ray absorptions
and emissions, end of the second part of this course, nuclear physics)

How come … 7
 How come we can’t
derive this from Modern Physics
Maxwellian waves?

waves or
particles?

How come
they are
characteristic the correct theory of matter
J.J. Thompson (1987) electron of atoms? at last

then applications,
8
PH 312
 Thomson’s Atomic Model

 Thomson’s “plum-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.

 In Thomson’s view, when the atom was heated, the electrons

could vibrate about their equilibrium positions, thus producing
electromagnetic radiation.

That is the dough or pudding in the plum pudding? the plums/raisins are the electrons
9
 What to do? Rutherford’s idea: shoot small but highly
energetic probes at atoms, see what happens,
Still done in particle physics today, also Rutherford managed to transform
one type of atom into another by shooting at them with α-particles

That is what physicists do, take things apart, figure out what its “internal
structure” is, how it works on the basis of this structure
Rutherford himself: “In Science there is only physics, anything else is
stamp collecting.” Various versions: ”The only real science is physics,
everything else is stamp collecting.”
10
11
 Experiments of Geiger and Marsden
 Rutherford conceived a new technique
for investigating the structure of matter
by scattering  particles from atoms.

 Marsden and Geiger showed that a few

 particles were scattered from thin gold-
leaf targets at backward angles greater
than 90°.

12
 Log-values No experiments for Z = 60
of y to (Neodymium) as it is rare and
cover cannot easily be beaten into very
many thin foils as the crystal structure
orders of is hexagonal close-packed, but
magnitude Ag (Z = 47) and Au, Cu, and Al
all can, because they are cubic
densest packed

Experimental
rule, change
only one thing
relationships of at a time
This will be form y = axk
important for appear as
Max Born’s straight lines in a
interpretation log–log graph,
of the wave slope = k
function

13
 4.2: Rutherford Scattering
 Scattering experiments help us study matter too small to be
observed directly.
 There is a relationship between the impact parameter b and the
scattering angle θ.

When b is small,
r gets small.
Coulomb force gets large.
θ can be large and the particle can be repelled backward.
Z1 and Z2 are the
repulsive charges in units
of the elemental charge e
In modern accelerators, kinetic energy K needs to treated relativistically 14
Rutherford Scattering
 Impact parameter b gets expanded into a circular area πb02 which is called cross
section.

 cross section σ = πb2 enters into relation for probability for a particle being
scattered by a nucleus
with n number of scattering
nuclei per unit area and t
thickness of the target foil

 Anything within a cross section area will be scattered to angles larger than θ0
.
15
 Rutherford Scattering Equation
 In actual experiment a detector is positioned from θto θ+ dθ that
corresponds to incident particles between b and b + db.

no h in these
equations, so
there are just
the correct
classical
treatment of
particles

 The number of particles scattered per unit area is

Where Ni is total number of
4.16 incident particles, K again
kinetic energy, r the angular
widths of the detector
16
 Shooting with the toughest bullets
at the weakest target, Rutherford’s
scattering theory broke down, this
means the underlying
assumptions are no longer valid,
from that one can determine the
size of the nucleus, still done
today for other particles in particle
accelerators

with k = 1/4π ε0

17
Order of magnitude correct ! Atoms are on the order of 1 to 3 Å (10-10 m)
 1908 Nobel prize in chemistry to Ernest Rutherford (later
Lord Rutherford of Nelson after the town where he was
born in New Zealand) and the physical chemist Frederic
Soddy, both at McGill University in Canada
for the radioactive transmutation of chemical
elements
14
N + α → 17O + p. 1917-1919 but that stable
isotope of oxygen was not identified until the 1930s
the alchemists’ dreams realized about 100 years ago, Glenn
Seaborg has produced several thousand atoms of gold from
bismuth, but at a big net financial loss.
"If your experiment needs statistics, you ought to
have done a better experiment."
"All science is either physics or stamp collecting" 
"The energy produced by the breaking down of the atom is a very
poor kind of thing. Anyone who expects a source of power from the
transformation of these atoms is talking moonshine." – 1933
"An alleged scientific discovery has no merit unless it can be explained to
a barmaid." 18
 Rutherford’s Atomic Model

 Rutherford proposed that an atom has a positively charged core

(nucleus) surrounded by the negative electrons.

Something three–dimensional where

there is a particle nucleus and particle
electrons in certain orbits, not correct

There is no positively charged dough or pudding in the plum pudding/raisin

19
cake, only raisins, empty space, and a core
4.3: The classical/solar system Atomic
Model is doomed
Let’s consider atoms as a quasi sun/planet model (only one planet so that
it is just a two body problem.
The force balance of circular orbits for an electron “going around” a
stationary nucleolus

For the centripetal

force in a circular orbit

where v is the tangential velocity of the electron.

Circular motion is accelerated, accelerated charges need to radiate
energy off according to Maxwell, loosing kinetic energy

20
Other weaknesses:
(1) gravity in the solar system is attractive, if there is
more than one electron in an atom, they will repel
each other.
(2) most importantly: if two solar system atom models
were to “collide”, they would form a “molecule model”,
but when that “molecule model” is broken up, there is
no physics that would ensure that the two original
“solar system atom models” would be obtained again.

21
 Balmer Series – hydrogen is the simplest
atom, so theoretical modeling starts there
 In 1885, Johann Balmer found an empirical formula for wavelengths of
the emission spectrum for hydrogen in nm within the visible range

nm (where k = 3,4,5…)

There is a minimum wavelength corresponding to

a maximum frequency and energy of photons

A good physical theory for H atom needs to make sense of this empirical result 22
 Rydberg Equation
 As more scientists discovered emission lines at infrared and ultraviolet
wavelengths, the Balmer series equation was extended to the Rydberg
equation, actually on the basis of this equation, people went out
looking for more lines :

Aside:

RH  R
me
 2 me c
R  
2h
1.09737 107 _ m 1
me  M

me  M

with μ as reduced
mass of the
elecron, α as fine
structure constant,
and M mass of the
Can be applied to isotopes of hydrogen by modifying R slightly nucleus 23
 4.4: The Bohr Model of the Hydrogen Atom
Niels Bohr’s general assumptions:
1) “Stationary states” (orbiting electron does not radiate energy) exist in
the hydrogen atom.
2) E = Einitial − Efinal = hf
3) Classical laws of physics do not apply to transitions between
stationary states, the electron just “jumps” makes a “quantum leap”
4) Angular momentum is quantized in units of h/2π , in the future simply
called h-bar

5) Correspondence principle, at very high quantum numbers (the indices
in (2)) binding energies become so low that transitions between
stationary states can be achieved without us noticing their discrete
quantum nature, energy changes seem to be continuous again
Nota Bene: All of these assumptions are consistent with the
assumption that the electron is a classical particle, as supported
by J.J. Thomson’s experiments and the rest of classical physics
except for the Maxwell equations
24
 e
v
r  
U  U r    F  dr 4 0 me r


without k bound system

just classical physics,

not good enough
new physics
has to be the same as
this r from classical
force balance, allows
n us to resolve for
v quantized condition for tangential
quantized energy
me r velocity and radius of orbit
levels, perhaps some later
homework or quiz question
n e

me r 4 0 me r

25
 radius of the hydrogen atom for stationary
states, n = 1, 2, 3, …

The smallest diameter of the hydrogen atom is

two times the Bohr radius ≈ 1 Å = 0.1 nm

 n = 1 gives its lowest energy state (called the

“ground” state), there is formally no E0
since quantum numbers start with 1 and
are positive integers

But some books may call it E0 nevertheless, E1 is also called 1 Rydberg ≈ 13.6
26
eV, needs to be divided by h and c in order to get the Rydberg constant in m-1
Transitions in the Hydrogen Atom
Lyman series
The atom will remain in the
excited state for a short time
before emitting a photon and
returning to a lower stationary
state. Most hydrogen atoms exist
in n = 1 at room temperature.
From previous
slide Balmer series (of formula fame)
E = Einitial − Efinal When sunlight passes through the
= hf emitted atmosphere, hydrogen atoms in
-3.4 - -13.6 = 10.2 water vapor absorb certain
wavelengths (visible), seen as
dark lines in absorption spectrum.
27
 If the material is very dilute there are
discrete spectra: Ångstrom (~ 1860)
last chapter, we learned that emission and absorption lines are at the
same wavelength
Very dense material, i.e. hot
“black body”, big-bang
1 background radiation, sun if
one does not look too carefully
There is typically more emission
lines than absorption lines,
because there are many more
possible transitions to go back to
lower state from a multitude of
2 excited states
Absorption lines are fewer in
number because there are
naturally only a small numbers of
atoms in exited states


reasonable model of an atom needs to explain these lines 28

 Optical Spectrometer and emission
spectra where d is
“line spacing
Note that on the
there is a diffraction
high grating”
voltage
rather than
a couple of
volts as in
the Frank-
Hertz gasses in tubes are typically
experiment quite dilute, discrete spectra
If highly excitated due to high tension, there are many different transitions
downwards, so typically more emission lines than absorption lines
 Spectroscopy can be done very precisely, in fact so precisely that isotopes
of hydrogen, were discovered that way, Deuterium as early as 1932, later
on also Tritium)
 Much depends on the quality of the grating …spectroscopic
measurements can be very precise, one can distinguish between
29
isotopes of hydrogen
Absorption spectra, light of certain wavelengths is taken out of the
“quasi black-body spectrum” of the sun, the glass prism provides a limited
dispersion so that the emission lines from the excited atoms in the sun are
not readily visible

It is typically only transition from the ground state to higher

states that are missing in the otherwise continuous spectrum
from the sun, so it is only a few 30
No need for special relativity / Fine Structure Constant

 The electron’s velocity in the Bohr model:

 For any state, n = 1, 2, ..

 v1 = 2.2 × 106 m/s ~ less than 1% of the speed of light.

 In any other orbit, there is less kinetic energy, i.e. the
electron needs to move even slower than that
 There is no need to use special relativity
 The ratio of v1 to c is known as fine structure constant.
It is dimension-less, so other
creatures in distant galaxies will
have it as well (will have the very
same numerical value for it) !!
α was actually introduced by Arnold Sommerfeld (nominated 81 times for
Nobel prize, didn’t win but died in a car accident) in his attempt to explain
spectral line doublets by elliptical electron orbits, confirmation of his
theory, just fortuitous, as his physics was as wrong as Bohr’s 31
discrete Hydrogen Atom Energy levels (after all it’s a bound system)
 The energies of the stationary states

where E0 = E1 = -13.6 eV (negative as all binding energies). Ground

state energy, also called one Rydberg of energy
 Emission of light occurs when the atom is in
an excited state and de-excites to a lower
energy state (nu → nℓ). Something negative minus
something even more
negative is positive, u for
upper, l for lower
where f is the frequency of a photon.

R∞ is the Rydberg constant for a

hypothetical nucleolus that is so heavy that it
remains stationary while the electron moves
around it, note that R∞ is a model concept32in
 The electron and hydrogen nucleus actually revolved about their
mutual center of mass.

 The electron mass is replaced by its reduced mass.

 The Rydberg constant for infinite nuclear mass is replaced by RH

for hydrogen, RD for deuterium, RT for tritium .

See also earlier slide where we

used α instead

All three hydrogen isotopes have a slightly different R values in

precision experiments, a way to detect these isotopes in the sun by 33
their “signature” on earth
 e 2
4 0  2 e2
R 
From Bohr’s
a0  
8 0 a0 h 2
model 4 0 c
me e 2
from Sommerfeld model
 2 me c
R   BUT Rydberg’s constant from high precision
2h experiment RH, very close but not exactly the same,
1.09737 107 _ m 1 how come?

To resolve: with μ as reduced electron mass

e e 
me  M and M as mass of the nucleus, in
RH  R
me me  M case of standard hydrogen it’s just
a proton, in case of deuterium a
mass of nucleus of one atom of proton and a neutron (beware
deuterium (2.0141102 u) is less than binding energy) in case of tritium a
an isolated proton (1.007825 u and an proton and two neutrons (again
isolated neutron (1.008665 u) added beware of binding energy) how
together (the rest is 2.224 MeV come? Special relativity says
binding energy with negative sign) so!)
34
Correspondence Principle in general

Classical electrodynamics + Bohr’s atomic model

some with an inconsistent

Determine the properties
classical mechanism
of radiation

Need a principle to relate the new modern results with classical

ones.
In the limits where classical and quantum
Bohr’s correspondence theories should agree, the quantum
principle theory must reduce the classical result.
That limit is quantum leaps between very
lightly bound electron states (very high
quantum numbers)
35
Bohr’s Correspondence Principle specific for
orbits of hydrogen atom
 The frequency of the radiation emitted fclassical is equal to the orbital frequency
forb of the electron around the nucleus.

 The frequency of the transition from n + 1 to n is

 For very large n only,

Substitute for E0:

From this idea he actually figured angular momentum needs to be 36
quantized in units of  for the mathematics to work out
 Limitations of the Bohr Model
The Bohr model was a great step towards a quantum theory of matter, explained the
spectral lines of hydrogen (and its three isotopes) comprehensively but it had its
limitations.

1) Works only for single-electron atoms and ions that have a single electron left. Only modification
in all equations Ze instead of e, where Z is the number of positive charges in the nucleus
2) Could neither account for the intensities nor the fine structure of the spectral lines (they are
actually doublets) for hydrogen when atoms were put into magnetic fields (Nobel prize to
Lorentz and Zeeman 1902)
3) Could not explain the binding of atoms into molecules
4) Contained unexplained quantum jumps – that’s not good physics, just a step in the right
direction, i.e. energy and other physical entities such as angular momentum in bound systems
need to be quantized

The reason for all of this is that the model is build on the basis of the particle
nature of matter.

37
 Z 2 E0 Within the three paper series by Niels Bohr in
En  
n2 1913, idea that electrons in other atoms are
arranged in shells with lots of empty space
1 2  1 1 between then, essentially correct
 Z R 2  2 
  nl nu 
Because we have
e2 in both E0 and
the Rydberg
constant
e2
R∞ 
8 0 a0 h 2
Unexpected lines in Details not
the sun’s spectrum correct
were identified to be
He+ (which also has
isotopes), i.e. different
effective mass
corrections for R 38
4.6: Characteristic X-Ray Spectra and Atomic
Number beyond hydrogen and one electron left ions
 Shells have letter names:
K shell for n = 1
L shell for n = 2

 The atom is most stable in its ground state, most atoms are in their
ground state at ambient conditions
An electron from higher shells will fill an inner-shell vacancy
at lower energy, when that vacancy has been created by
any sufficiently energetic process in the first place

 When it occurs in a muti-electron atom, radiation is emitted as an X

ray photon.
 It has the energy E (x-ray) = Eu − Eℓ.
39
Atomic Number Z

L shell to K shell Kα x-ray

M shell to K shell Kβ x-ray

 Atomic number Z = number of protons in the nucleus (6 for

carbon, 7 for nitrogen)
 Moseley found relationships between the frequencies of the
characteristic x-ray and Z.
This holds for the Kα x-ray.

Why is b = 1? There are two electrons in the lowest orbit in all elements 40
except H, one is left and shields the nucleolus if the other is removed
 Why not Hg?

Because of its Kβ less intense

high intensity, it
makes sense to
than Kα, more
use only Kα X- electrons jump
rays (nearly down from L
monochromatic) shell compared
for X-ray to M shell, Kβ
crystallography
more energetic

Kα and Kβ, slightly different An

Now with a generalization of Bohr’s H-model, we have a “reasonable” theory
41
of matter (atoms) that can to some extend explain this peculiar behavior !!
Moseley’s Empirical Results
 The most intense Kα X-ray is produced by transition from n = 2 to n = 1

valid for whole K series, R is

again Rydberg’s constant, as this
is a “modified Rydberg equation”,
which can be explained on the
basis of the Bohr-shell-model of
multi-electron atoms and the idea
of shielding
Moseley’s research clarified the importance of the by a single
electron shells for allremaining
the
elements (except hydrogen which has only 1 electron
electron)inand
the beyond
K shell Mg (Z
= 12) for practical reasons.
For a vacancy in the K shell to be filled by an electron from the L shell (and
assuming that two electrons can occupy the K shell at most), the electron
that “jumps down” sees the nuclear charge reduced (shielded) by the 1
remaining electron

42
 Note that the ratio of the radii is not correct

Sulfur, Z = 16

Note that there are 8

electrons in the L shell,
we will later on
understand how come
9 if generalized Bohr H model would work

Empirically for Lα series 43

There are also other processes, emission of Auger electrons to reduce an exited
atom’s energy, again what we detect is quantized energy levels in bound systems,
these spectra test the energy of the outermost electrons, so are sensitive to the
valence in compounds, ultra clean surfaces, i.e. ultra high vacuum is required

44
R ≈ R0 A0.3333 with R0 = 1.2 10-15 m and A = Z + N

45
 also for He+. Li++
Better to call it E1

particularly important for Kα

lines, then b = 1

46
 http://www.kokogiak.com/megapenny/fourteen.asp

A real
quantum
jump would
be adding
or taking
away one
penny from the “war on terror”
such a has cost about $1
cube trillion so far
(2010), but as
wars go that one
accounts only for a
few % of the
annual GDP since
9/11
http://www.fas.or
g/sgp/crs/natsec
1,000,000,016,640, one trillion, sixteen thousand six hundred /RS22926.pdf
and forty Pennies [one cube measuring 273 x 273 x 273 feet ]

47
 http://www.kokogiak.com/megapenny/seventeen.asp

A real Sure “quantum

quantum jumps” in
jump would macroeconomic
be adding and “bankstering”
or taking are not based on
away one the quantum
penny from jumps physicists,
such a other natural
cube scientists, and
engineers are
talking about

1,000,067,088,384,000, One quadrillion, sixty-seven billion, eighty-eight million,

three hundred and eighty-four thousand Pennies, [ One cube measuring 2,730 x
2,730 x 2,730 feet ]
48
 $1 million

$100,000

other cubic stacks of pennies, always remember what a quantum jump

really is, Francis Scott Fitzgerald to Ernest Hemmingway: “the rich are
different from you and me”. 49