UNIT 2: ATOMIC STRUCTURE

EARLY ATOMIC THEORIES

Our concept of the atom has changed over the course of history. As technology
advanced so has our understanding of the structure of the atom. Biological cells are
large enough to study using microscopy, but atoms are too small to study, so the best
we can do is interpret experimental findings using models. Every time more information
is found the model is modified and so the model of the structure of an atom has
changed repeatedly over the past 200 years and will likely change many more times
in the next 200 years . Understanding the history of the atom will help you appreciate
the fact that the structure of the atom is a "work in progress".

The word atom comes from the Latin, "atomos" which means indivisible. Atoms are the
fundamental building block of all molecules as cells are the fundamental building blocks
of the living world. An atom was considered to be a particle that had mass and a
specific size and behavior, although none of these was known. It wasn't until the early
1800's when John Dalton used the "scientific method" approach of investigation to
propose the first atomic theory. His concept of the atom has often been referred to as
the "billiard ball" model, in that the atom was a very small, solid particle with specific
properties.

From the work of Coulomb, Faraday and the invention of the cathode ray tube by
Crookes it was discovered that the atom consisted of smaller sub atomic particles that
possessed charge. In 1900, Thomson 's model of the atom portrayed a solid particle of
positive charge, with numerous negative charges embedded in it such that the overall
atom was neutral. This has often been compared to a "raisin bun" or with the dough
representing the positively charged matter and the raisins would be the electrons
embedded in the positive portion. The famous oil drop experiments by Millikan
determined the charge of one of these negative particles, now called an
electron.
With the discovery of radioactivity and alpha particles, Ernest Rutherford performed
his now famous "gold foil experiment". He bombarded a thin piece of gold foil with
alpha particles (a helium atom without orbiting electrons). To his amazement a small
number of these alpha particles did not travel through the gold foil, some were
deflected at various angles and some bounced straight back, similar to a ping pong
ball bouncing off a wall . Based on these observations Rutherford proposed the
following new "nuclear" model:
1. The atom consisted of a large portion of empty space. This accounts for most of
the alpha particles going through the gold foil paper .
2. The "positive" charge was found condensed in the centre of the atom, in the
nucleus. This accounts for the alpha particle bouncing back. The small dense
positive charge of the nucleus could repel the positively charged alpha particle
with enough force that it reversed its direction.
3. The electron(s) are located somewhere in the remaining empty space of the
atom.
The fact that the electrons were in a location “somewhere" obviously left the
question of where was somewhere. To properly understand bonding of atoms we
need to know where the electrons are.

Evidence for the existence of the proton was gathered in 1914 when Rutherford, Thomson,
and associates studied positive rays in a cathode ray tube and found that the smallest
positive charge possible was from ionized hydrogen gas. The charge and mass of the proton
were determined by bending the hydrogen-gas positive rays in a magnetic field. The proton
was shown to have a charge equal to but opposite to that of the electron and a mass
1836 times that of an electron. All of this work was done in gas discharge tubes that evolved
into a version of the mass spectrometer developed by Francis Aston between 1919 and
1925. Evidence from radioactivity and mass spectrometer investigations falsified Dalton's
theory that all atoms of a particular element were identical. It was found that atoms of the
same element had different masses. These were called isotopes. Their existence became
clear when Chadwick discovered neutral particles called neutrons.

Before moving further we need to understand a little bit about the nature of matter and
energy.
The Nature of Matter and Energy

The nature and properties of light have been investigated for centuries, right from the time of
the Greek philosophers. In the mid 19th century, Maxwell put forth the theory that light is an
electromagnetic wave composed of continuous wavelengths that form a spectrum. This
theory became widely accepted and light and matter were thought to be separate from
each other.

At the end of the nineteenth century, the idea prevailed that matter and energy were
distinct. Matter was thought to consist of particles, while energy was described as a wave.
Particles were things that had mass and whose position in space could be specified. Waves
were described as having no mass and their position in space could not be specified. It
was also assumed that there was no intermingling of matter and light.

In 1887 Hertz discovered the photoelectric effect (light shining on a metal causes electrons
to be emitted from the metal). According to the existing theory of the time, a brighter
(more intense) light should have led to the emission of electrons with greater K.E. But this
was not the case. Hertz found that electrons were emitted from the metal only after the
light reached a certain threshold frequency. Hertz could not explain his observations, and
so the theory came to be viewed as flawed.

An explanation came at the beginning of the twentieth century. The first important
advance came in 1901 from the German physicist Max Planck. Studying the radiation
profiles emitted by solid bodies heated to incandescence. Planck found that the results
could not be explained in terms of the physics of his day, which held that matter could
absorb or emit any quantity of energy. Planck could only account for these observations by
postulating that energy can be gained or lost only in whole-number multiples of the
quantity hf, where h is a constant called Planck's constant, determined by

experimentation to have the value 6.626 x 10-34 J s. Thus the change in energy for a
system, E can be represented by the equation:
E = nhf
where n is an integer (1 , 2, 3, ...), h is Planck's constant, and f is the frequency of the
electromagnetic radiation absorbed or emitted.
Now energy seemed to have particulate properties. Each small ‘packet’ of energy is called
a quantum, and a system can transfer energy only in whole quanta. The next important
development came from Albert Einstein when he proposed that electromagnetic radiation is
itself quantized. He suggested that electromagnetic radiation can be viewed as a stream of
‘particles’ called photons. The energy of each photon is given by the expression:
hc
E photon  hf  ,

where h is Planck's constant, c is the speed of light, f is the frequency of the radiation, and 
is the wavelength of the radiation.

Einstein went on to prove that matter and energy are not distinct, and show the same
types of properties. All matter exhibits both particulate and wave properties. Large pieces
of matter, like tennis balls exhibit predominantly particulate properties. The wavelengths
associated with them are too small to be observed. Very small pieces of matter, like
photons, while showing some particulate properties, exhibit predominantly wave
properties. Pieces of matter with intermediate mass, like electrons, show clearly both
particulate and wave properties.

Electromagnetic Radiation

One of the ways that energy travels through space is by electromagnetic radiation. The light
from the sun, the energy used to cook food in a microwave oven, the X-rays used by
denti sts, and the radiant heat from a fireplace are all examples of electromagnetic
radiation . Although these forms of radiant energy seem quite different, they all exhibit the
same type of wave-like behavior and travel at the speed of light in a vacuum.

Waves have 3 primary characteristics; wavelength ( - lampda) is the distance between two
consecutive peaks or troughs in a wave, frequency (f) is the number of waves (cycles) that
pass a given point in space in one second (measured in hertz, Hz), and speed. All
electromagnetic radiation travels at the speed of light (c = 3.00 x 108 m/s). Consider the
figure 1 below:
 Figure 1: The nature of waves.

Notice that the wave with the shortest wavelength has the highest frequency and vice
1
versa. This implies an inverse relationship between wavelength and frequency, i.e.   , or
f
f  c
where  is the wave length in meters , f is the frequency in cycles per second, and c is the

speed of light (3.00 x 108 m/s) . In the SI system cycles i s understood and the unit
becomes 1/s, or s -1, which is called the hertz (abbreviated Hz).

Now let’s continue with Atomic Theory

THE BOHR ATOMIC THEORY
Rutherford's model of a nuclear atom was a significant advance in the overall understanding
of the atom, but it had a few problems. Rutherford considers an atom to consist of a
positively charged nucleus with electrons revolving around it. The electrons and the nucleus
in an atom are held together by electrostatic force of attraction. Because of the presence of
electrostatic attraction between the nucleus and the electrons, the electrons should fall into
the nucleus. But it does not happen. In order to explain this, Rutherford postulated that the
electrons are not stationary, but are revolving around the nucleus, and the attractive forces
between the nucleus and electrons are balanced by the centrifugal force acting only the
moving electrons.

Rutherford’s model explains the structure of atom in a very simple way. But, it suffers from the
following drawback:
An electron revolving around the nucleus gets accelerated towards the nucleus. According
to the electromagnetic theory, an accelerating charged particle must emit radiation, and
lose energy. Because of this loss of energy, the electron would slow down, and will not be
able to withstand the attraction of the nucleus. As a result, the electron should follow a spiral
path, and ultimately fall into nucleus. If it happens then the atom should collapse in about
10-8 second. But, this does not happen: atoms are stable. This indicates that there is
something wrong in the Rutherford model of atom.

In order to address these drawbacks, Bohr used the quantum theory developed by Planck
and Einstein. When a current was passed through hydrogen gas sealed in a glass tube
(gas discharge tube) only certain frequencies of light were emitted giving line spectra as
shown in figure 2. Bohr reasoned that if the light released or absorbed from an atom was
quantized, then the energy of the electron inside the atom must also be quantized. In
other words, an electron can only have certain energies. The simplest arrangement
would be a planetary model with each electron orbit at a fixed distance and with a fixed
energy. This meant that the electrons could not have any energy, other than the allowed
quantized energies. Bohr stated that these were special energy states (called stationary
states), and the existing rules of physics did not apply inside an atom. Electrons do not radiate
energy as they orbit the nucleus. Each orbit corresponds to a state of constant energy
(called a stationary state).
 Figure 2: Line spectra emitted by hydrogen gas

Bohr also proposed that the electron in a hydrogen atom moves around the nucleus only in
certain allowed circular orbits. An electron can only move from one orbital to another, never
between orbitals. Therefore only certain energies can be absorbed and transmitted. Bohr
calculated the radii for these allowed orbits using the theories of classical physics and by
making new assumptions. Experimental data was collected and the energy levels and
equations to calculate energy differences between orbitals were derived.

When Bohr passed a current though hydrogen gas electrons were excited into higher
energy levels. When the electrons returned to lower energy levels, light was released. The
light released corresponds to the energy lost as the electron moves to a lower energy
state. The frequency of the emitted energy is related to the energy difference between
the two orbitals. The difference in energy between two orbitals would be the energy
required to excite an electron between the two shells (absorption spectra), or the
energy released when an excited electron moves from a higher energy level to a lower
one (transmission or emission spectra) as shown in Figure 3.
.
 Figure 3: Electronic transitions in the Bohr model of the hydrogen atom

Drawbacks of Bohr’s Theory

1. The theory only worked for hydrogen, and for no other element. The spectra of larger
atoms are considerably more complicated than that of hydrogen, but generally a
characteristic spectrum is seen. When applied to multi-electron atoms, several series of
lines were seen that should not have been there. These extra lines were given names:
Sharp, Principle, Diffuse, Fundamental

2. Bohr was also wrong in thinking that an electron’s position and motion can be specified at
a given time, as well as thinking that orbits have fixed radii.

Successes of Bohr’s Theory

This orbital model of the atom explained the trends (listed below) within the periodic
table developed by Mendeleev.

The number of energy levels containing electrons equals the row number (or period)
of the element.

The number of valence electrons in an atom equals the group number (or family) of
the element

The maximum number of electrons in each energy level equals the number of
elements in each period. (i.e. 2,8,18; Only useful for the first 20 elements)
BEYOND THE BOHR ATOMIC THEORY: THE QUANTUM MECHANICAL MODEL

Werner Heisenberg, Louis de Broglie, and Erwin Schrodinger worked together to put
forward the quantum mechanical model of the atom. The main difference lies in the
behaviour of the electron. De Broglie suggested that if light can behave as if it were
composed of particles, then perhaps particles can have properties that are associated
with waves.

It was known that the energy of a particle of mass m is E  mc 2 , where c is the speed of
light in vacuum.

It was also known that the energy of a photon is:

hc
E  hf or E 


For the same radiation, the energy of the particle must be equal to the energy of the
wave. Therefore:

E particle  Ewave

hc
mc 2 


h
therefore 
mc

For a particle (e.g. electron), c is replaced with the velocity, v, of the particle. Hence the
wavelength of a matter wave (the De Broglie wavelength) is given as :

h
 particle 
mv

Experimental evidence for this wave-particle duality comes from observations that
electrons can be bent or diffracted (a property that only waves possess).
According to Schrodinger and De Broglie an electron around a nucleus resembled a
standing wave as seen in figure 4 below.

Figure 4: Depiction of Standing Waves

The electron was considered to be a circular standing wave around the nucleus. The
waves have wavelengths that are whole numbers. Only certain shells have
circumferences that will accommodate a whole number of wavelengths. This whole
number is the principle quantum number (n = 1, 2, 3…). Figure 5 shows how this works.

Figure 5: The Hydrogen Electron Seen as a Standing wave around the nucleus

At this point Heisenberg realized that it was impossible to know the speed and the
position of the electron simultaneously. This is called the Heisenberg Uncertainty Principle.
This principle is irrefutable and Bohr’s model fails to obey it. Given this uncertainty all that
could be done was to determine the probability of locating an electron in a specific
region in space. Schrodinger used mathematical equations to describe the behaviour of
the electron as a wave. A solution to these equations gives specific wave functions
(called orbitals…NOT orbits).

The wave function or orbital gives us an idea of where the electron is likely to be found.
The orbital is an area where there is a high probability of finding an electron. Wave
functions have allowed physicists to create electron probability density plots (Figure 6)
that show regions around the nucleus with the greatest probability of finding an electron.
 Figure 6: Probability Distribution of the Hydrogen Orbital

Orbital are not all circular (or spherical). They have different shapes. Figure 7 shows how
orbitals surround a nucleus. The orbitals overlap and an electron can jump to any orbital
if it absorbs enough energy.

Figure 7: Probability Distribution of Various Orbitals around a Nucleus

This is a pretty concise video, although it does contain some material that we have yet to
learn. Enjoy.
https://youtu.be/agjG7kgixJs History of atomic structure