Science/Chemistry/CHEM1031 and CHEM1051

Atomic Spectroscopy
Blackman 3rd ed. Chapters 4.1 – 4.5, 4.6 – 4.9, 5.1, 5.2

Dr. Kim Lapere

Wks 1—3

http://drlapere.participoll.com/
 Copyright notice
Some images used in these lectures are taken, with permission, from “Chemistry 2nd ed.”,
Blackman et al., (Wiley, 2012); and other sources as indicated, in accordance with the
Australian copyright regulations.

All of these lecture notes are made available to UNSW students through Moodle.
These lecture notes may not be posted on any other website.

1
 Syllabus
• Atomic spectroscopy, Hydrogen spectrum, Rydberg equation.
• Quantum mechanical principles and the quantum mechanical model of the atom.
Orbitals and quantum numbers from the Schrödinger equation.
• Electronic configurations of atoms; Pauli exclusion principle, Hund's rule. Electronic
configurations and the periodic table. Configurations of ions. Diamagnetic and
paramagnetic species. Isoelectronic species. Periodicity of atomic and ionic sizes,
ionization energies and electron affinities.

2
 Learning outcomes
 Calculate wavelength from frequency and vice versa for electromagnetic radiation.
 Use the Rydberg equation to calculate the wavelengths emitted or absorbed by a H
atom.
 Calculate photon energy for EM radiation from its frequency.
 List the allowed values of the quantum numbers for orbitals in hydrogen–like atoms.
 Sketch the shapes of s, p, and d orbitals.
 Write ground–state electron configurations for all main group elements and first–row
transition metals and ions of these elements using 'arrows in boxes' and '1s1' notation.
 Identify isoelectronic species and predict relative sizes of these species.
 Predict the magnetic properties of isolated atoms and ions.
 Predict relative sizes, ionization energies, electron affinities and electronegativities of
atoms based on position in the periodic table.

3
Atomic spectroscopy
Using light to probe atoms:

Each element has a unique pattern that provides valuable clues about its structure.
Light
Light is only a small part of the electromagnetic radiation spectrum:
Electromagnetic radiation (EMR)
EMR is used to study structure – how light interacts with atoms tells us a lot about the
properties of the atoms.

What is EMR?
o Electric and magnetic fields at right angles to each other, propagating through space-
time

By SuperManu - Self, based on Image:Onde electromagnetique.png, CC BY-

SA 3.0, https://commons.wikimedia.org/w/index.php?curid=2107870
 Electromagnetic radiation (EMR)
• Refraction
– rainbows!

Wave-like properties
© David Parker

• Diffraction - CDs • Interference

Spectrum of fluorescent
lamp by diffraction in a
CD (Photo: Tim Jones)

© Thomas Mittiga, from

http://laser.physics.sunysb.edu/~tmit/interference.html
By Wisky - Own work, CC BY-SA 3.0,
https://commons.wikimedia.org/w/index.php?curid=15113998
Properties of light
• Wave-like:
• Regular oscillation e.g. position of duck on surface
• Light waves vary with time (snapshot)

Frequency  is the number of wave crests (or troughs)

per second. The wavelength  is the distance between
successive wave crests (or troughs).

• The duck will bob at the top of the wave 4 times in 1

second, so the frequency is = 4 s-1 (or Hz).
• The wavelength of the wave decreases as the
frequency increases (figures from top to bottom) i.e.
frequency and wavelength are inversely proportional.
 Properties of light
Amplitude determines intensity:

Phase refers to the starting position of the wave:

When waves have the same phase (and amplitude and wavelength) they will look exactly the same when superimposed (layered
over each other). Since (b) is exactly the opposite phase of (a) the result would be (c).
 Properties of light
Amplitude determines intensity:

Phase refers to the starting position of the wave:

In the shaded region there is exactly 1 wavelength. The yellow spot highlights the same position of the wave – in (a) it is at ½ λ,
however in (b) it is at 1 λ. These two waves are out of phase by half a wavelength.
The speed of light
Light waves, and all other types of EMR, always move through a vacuum at the same
speed.
In a vacuum c = 2.998 x 108 m s‐1

λν = c
Wavelength (distance) × Frequency (time) = Speed of light (velocity)
m  × s‐1 =  m s‐1
Worked example λν = c
An FM radio station transmits its signal at 88.1 MHz. What is the wavelength of the signal?

c = 2.998 x 108 m s-1

λ = 88.1 MHz ( = 88.1 x 106 Hz)

Rearrange for wavelength:

2.998 10
3.40
88.1 10

Radio waves are in the order of m so this checks out!

Think critically!
What is the frequency of X-rays that have a wavelength of 5 nm?
Assume the x-rays are in a vacuum, so use c = 2.998 x 108 ms-1
Light behaves as a particle?
Light can behave not only as waves, but also as particles. This is known as wave-particle
duality.
In 1905 Albert Einstein postulated that light comes in ‘packets’ or bundles called photons.
His theory accounts for the photoelectric effect observed by Heinrich Hertz in 1887:
shining light (of a high enough frequency) onto the surface of a metal would eject electrons.

Image: http://en.wikipedia.org/wiki/Heinrich_Hertz
Photoelectric effect
Further experiments showed:
1. Current would flow if the light had a
frequency above a certain threshold
value, ν0a and ν0b, that was characteristic
of the metal used (a or b)
2. No current would flow using light below
the threshold frequency - no matter how
intense it was
3. The current measured when the
frequency used was greater than the
threshold frequency depended upon
the intensity of the light
4. The energy of the electrons ejected
from the metal (i.e. the current) depended
upon the frequency of the light.

Threshold frequency indicates a certain amount of energy is required to remove an electron

from an atom of the metal(s).
Light behaves as a particle?
The energy of photons are directly proportional to their frequency:
E = hν
Where:
E = energy (J)
 = frequency (s-1 = Hz)
h = Planck’s constant = 6.626 x 10-34 J s

[Wikipedia] From left to right: W. Nernst, A. Einstein, M.

Planck, R.A. Millikan and von Laue at a dinner given by
von Laue in Berlin on 11 November 1931
Light behaves as a particle?
The energy of photons are directly proportional to their frequency:
E = hν
Where:
E = energy (J)
 = frequency (s-1 = Hz)
h = Planck’s constant = 6.626 x 10-34 J s

Therefore only photons with enough energy can allow electrons to

break free from the attraction of the metal nuclei. (Threshold
frequency)

Any excess energy from the photon (greater than the binding
energy) is converted to kinetic energy once the electron is ejected.
 Light behaves as a particle?
E = hν
Positive energy

Negative energy
when bound
Worked example
What is the energy of red light that has a wavelength of 655 nm?

1. Convert red wavelength to frequency using c = νλ

2.998 10
4.58 10
655 10

2. Determine energy using E = hν

6.626 10 4.58 10
3.03 10
Think critically!
Does red light or blue light have more energy? Use the following wavelengths:
Red = 700 nm
Blue = 470 nm
Electron energies

Free, moving electrons have kinetic energy. The

energies these electrons can have are
continuous, as seen from the photoelectric effect
experiment.
Classical mechanics
What about the energies of electrons that are
bound in atoms?

Quantum mechanics
Interaction of light and matter
White (polychromatic) light passing through a gas composed of single atoms of one
element (e.g. H) will show a spectrum with a range of wavelengths, like below.
Why are there thin black lines in the spectrum?
What do the lines correspond to?
Interaction of light and matter
White light has photons with a range of wavelengths (polychromatic). When they pass
through the gaseous atoms some of the photons’ energies (i.e. specific frequencies)
exactly match the difference between energy levels of an atom. These photons are
consequently absorbed, leading to no light of that frequency/wavelength showing on the
detector (i.e. the black lines).
Quantisation
This pattern is known as an absorption spectrum; light
of specific frequencies has been absorbed by
atoms, causing the black lines.

Specific frequencies/energies are being absorbed by the

atom. This indicates the energies available in an atom
are non-continuous. Rather, there are discrete ‘steps’
of energy available, like rungs on a ladder. The energy is
restricted to certain levels, known as quantisation.

When an atom absorbs energy from photons, its only

those photons with the same frequency/energy as the
energy levels the atom contains (taking a step).

Diamond Tree fire lookout. 52 m high.

Top photo: © John Zaitseff 2011.
Emission
A similar experiment where gases were heated by an electrical discharge (current passed
through) produces light at specific frequencies (lines). Since light was emitted by the
gaseous atoms the spectrum produced is known as an emission spectrum.
Emission
Like absorption, the emission lines correspond to exact energy level differences in the
gaseous atoms however now they are due to a photon of specific frequency/energy being
emitted instead of absorbed. It’s the exact opposite of absorption.
Colours in fireworks

https://en.wikipedia.org/wiki/Fireworks
Worked example 4.4
What is the energy change when the electron in a hydrogen atom undergoes a transition
from the fourth energy level to the second energy level? What is the wavelength of the
photon emitted?
Use E4= –1.36 x 10–19 J and E2= –5.45 x 10–19 J

E4 –1.36 x 10–19 J
Final - initial
E3

E2 –5.45 x 10–19 J

E1
Worked example 4.4
What is the energy change when the electron in a hydrogen atom undergoes a transition
from the fourth energy level to the second energy level? What is the wavelength of the
photon emitted?
Use E4= –1.36 x 10–19 J and E2= –5.45 x 10–19 J

E4 –1.36 x 10–19 J

E3

E2 –5.45 x 10–19 J

E1

Or 486 nm
Energy level diagram
 Ground and excited states
Ground state of an atom is one in which it has the lowest (most stable) energy.
Excited states are any energy level higher than the ground state (unstable). Excited atoms
subsequently give up their excess energy (i.e. emit photons or in collisions) to return to a
lower energy state (eventually ending back at the ground state).

http://www.mdpi.com/molecules/molecules-17-04047/article_deploy/html/images/molecules-17-04047-g001-1024.png
Hydrogen’s atomic energy levels
A hydrogen atom has a regular
progression of quantised energy levels
(other atoms do too but it gets
complicated with more electrons).
Energy levels become increasingly closer
in energy (bunch together) the further they
are from the nucleus. Beyond these
energy levels the electron is no longer
bound by the nucleus and the atom has
been ionised.

n=
Hydrogen’s atomic energy levels

As energy levels approach n =  the energy differences between them become smaller.
Since energy and wavelength are inversely proportional the spectrum here has the
lines converging the opposite to the energy level diagram.
For example the transition at 656 nm (red) is due to the smallest transition in the Balmer
series (En = 3 → En = 2).

Principal
quantum number
Balmer series
Swiss mathematican and high school teacher Johann Balmer
discovered in 1885 a mathematical relationship which was able to
describe each of the emissions of the hydrogen atom.

The visible parts of the hydrogen atomic spectrum in the Balmer

series (consisting of the wavelengths 410 nm, 434nm, 486 nm and
656 nm) are shown below. Lines five and six can be seen with the https://en.wikipedia.org/wiki/Johann_
Jakob_Balmer
naked eye but are considered to be UV (< 400 nm).

410 nm 434 nm 486 nm 656 nm

© Jan Homann, 2009, Visible Spectrum of Hydrogen

https://en.wikipedia.org/wiki/Balmer_series
Rydberg equation
The Swedish physicist Johannes Rydberg (1854–1919) subsequently
restated and expanded Balmer’s result in the Rydberg equation:

Rydberg constant = 1.097 x 107 m-1

By Per Bagge (1866-1936) -

Original photograph in the
collections of The Archives and
wavenumber Museum of the Academic Society
in Lund, Sweden., Public Domain,
https://commons.wikimedia.org/w/i
ndex.php?curid=41525001

This equation relates the wavelength of a photon absorbed or emitted

to the transition between two energy levels of a hydrogen atom.
Rydberg worked example
What absorption wavelength corresponds to a n=1 to n=5 transition?

1/ = -RH x (1/52 – 1/12)

= -1.10 x 107 x (1/25 - 1)
= 1.05 x 107 m-1

 = 9.49 x 10-8 m

(= 95 nm)
Ionisation energy
How much energy is required to completely remove an electron from a hydrogen atom?
The removal of an electron from a neutral atom is called the ionisation energy.

* Rydberg constant in J instead of m-1