Atomic Spectroscopy

1. Why study atomic spectra?

Atomic spectroscopy involves the study of the absorption and emission
of photons (light) by atoms. Why is this a fundamentally important field?

Physicists disparagingly refer to chemistry as “the study of electrons”.

Well, electrons are crucial in chemistry. Electrons are shared when
atoms form bonds:
F+ F → F2
Electrons are lost when molecules are ionized:
N2 + uv light → N2+ + e-

The electron configurations of atoms, which change as we move around the

periodic table, critically determine an elements properties.

Sodium (Na) is highly reactive [1s2 2s2 2p6 3s1] yet neon (Ne) is largely
unreactive (inert) [1s2 2s2 2p6].
To understand an atom or molecule’s chemistry we need to understand how
its electrons are arranged – this information comes from atomic
spectra.

More fundamentally, information from atomic spectra stimulated the

development our current ideas of: orbitals, spin, quantum numbers,
angular momentum.

In fact, the experimental observation of atomic spectra prompted the most

important idea in science in the 20th century, that “energy is quantized”.

This idea lead to the development of

quantum mechanics.

To understand bonding we need to

Photon energy
understand how electrons are arranged in
One of the series observed in the atomic
atoms: atomic spectra. spectrum of hydrogen
2. The fundamental principle of spectroscopy

The fundamental principle of spectroscopy stems

from the fact that atoms and molecules can only
possess energy (electronic, rotational,
vibrational) in quantized, not continuous,
amounts

Typically there is an equation which governs

which energies are possible for a given
species.

We will see that the equation for the electronic

energy states (orbitals) of the hydrogen atom is:
E =−hc R
n
H
2
in Joules
where h is Planck’s constant, c is the speed of
light, RH is the Rydberg constant for the H atom.
Often in spectroscopy we use units other than Joules for the energies of
atomic and molecular levels to get “nice” numbers.

When a hydrogen atom re-arranges its electrons to move between two levels
it emits or absorbs a photon with an
energy equal to the separation of
the levels:

Photon Energy = E2-E1= hv

By measuring the energies of the photons

that atoms emit or absorb we are learning
about their electronic energy levels
and hence their electronic structure.

So how do we measure an atomic

spectrum?
3. Experimental Aspects
There are two general types of spectroscopy:

Absorption spectra: measure the wavelengths of light

that are absorbed by a sample.

Here the atoms are taking up energy and moving to

higher lying energy levels.

Emission spectra: we put energy into the sample of atoms

(heat, electrical discharge) and excite them to higher
energy levels.
We then measure the wavelengths of light that are emitted
as the atoms return to lower energy levels.

In these spectra the atoms are giving up energy.

A typical absorption spectroscopic experiment will look like:
Light source: must produce a
broad range of wavelengths
of light for the atoms to
absorb

Sample: normally gaseous,

often this means we need to
heat the sample.

Wavelength-selecting element: to see which wavelengths (energies) of

light are absorbed we need to “disperse” the light that has passed
though the sample. One can use a prism or a diffraction grating.

Detector: The position of the light at the detector tells us the wavelength,
Traditionally the detector was a photographic plate. Modern experiments
may use highly sensitive cameras or rotate the wavelength selecting
element and use a point detector.
In an emission spectroscopic experiment we do not need the light source but
have to excite the atomic sample and monitor the wavelengths of light
emitted.:
4. Atomic spectra: what do we see?
Atomic spectra consist of lines, showing the
electronic energy of atoms is quantized, that
atoms have energy levels.

Different atoms have different patterns of lines.

Atomic spectra can be used to identify different
atoms.

Atomic spectroscopy shows that iron atoms are

present in the sun’s atmosphere.

We will consider the atomic spectrum of hydrogen

(H). We need first of all to review some of the
properties of light
(electromagnetic
radiation)
5. Electromagnetic radiation

Visible light is only part of the electromagnetic

spectrum which extends from radio waves at low
frequency to gamma-rays and x-rays at high
frequency

Some properties of light are easiest to understand

we consider light as a wave (diffraction) and some
properties are easiest to understand if we picture
light as a stream of particles (photoelectric
effect).
 5.1. Key facts about electromagnetic radiation:
1. The energy of electromagnetic radiation is quantized. Light behaves
as if made up of packets of energy (photons) with an energy E=
hf

Example calculation: What is the energy of a photon of red light

f=4.2 x 1014Hz and blue light f=7.5 x 1014 Hz

E=hf so for the red light E= 6.626 x 10-34 x 4.2 x 1014 = 2.8 x 10-19 J
Remember (AS) 1 eV = 1.602 x 10-19 J so E = 2.8/1.602 = 1.7 eV

For blue light E= 3.1 eV

2. The speed of light in a vacuum is a fundamental constant:

c= 2.99 792 458 x 108 ms-1 ≈ 3 x10 8 ms-1
One can think of this as the speed of the photons or the
speed of the wave.