Spectroscopy Basic Concepts

SPECTROSCOPY Spectroscopy is the science of
Basic concepts spectra, i.e. it involves a measurement

part 1 of a property that is a function of the
frequency of the light
Umeå 2006-04-10 Bo Karlberg
Light = electromagnetic radiation
Frequency = the number of a

repeatedly occurring event per
time unit
Example: Frequency = 2/s (2 Hz)

Wave
Våg
1 2 wavelength
Time or distance
1 second
Definition of wavelength, λ
1
What about the wavelength of light?
The wavelength depends on the type of

radiation we take into account
λ for visible light is in the range 380-780 nm
nm = nanometer, i.e. 10-9 m (one thousandth

of a micrometer)
What about the wavenumber of light?

Conversion of nm to cm-1
(and vice versa)
In spectroscopy we usually express

frequency in the unit wavenumber,
the dimension is cm-1 (reciprocal cm)
cm-1 = 107 / nm
nm = 107 / cm-1
Exemple:
Light is a wave motion but can also
be regarded to be a stream of
2500 nm – how many reciprocal cm? photons.
All these photons have an energy
that is defined by the wavelength of
cm-1 = 107 / 2500 = the light.
10000000/2500 = 4000
2
• An X-ray photon or a UV
photon can degrade chemical
compounds
An X-ray photon has a high • A photon in the visible range
energy whilst a radiowave photon can change the electron structure
has a low energy. of a chemical compound
• A photon in the IR range

accomplish vibrations and
rotations of molecules
Thus:
Wiens law:
λmax T = b A hot body radiates photons
with high energy while a cold
body radiates photons with
where T is the absolute temperature and
b is a constant low energy
Exemple: sun – earth Exemple: sun – earth

The inner temperature of the This is explained by the fact
sun is several billions degrees. that the surface temperature
This corresponds to lethal X-ray is about 6000 K.
radiation. However, our
The atmosphere is transparent
experience is that the sun
to visible light. The ozone
emits yellow light, i.e. light in
layer absorbs parts of the UV
the visible range.
light.
3
The average temperature of Normally, the sum energy of
the earth’s surface is about incoming radiation = sum
20 C or 300 K. energy of outgoing radiation
The earth emits IR radiation
to the universe

The greenhouse effect?? An astronaut in outer space
The earth emits IR-radiation that ”sees” the carbon dioxide-
is absorbed by carbon dioxide and water layer of the earth – not
water in the atmosphere. the surface. This layer is
significantly colder than the
These species absorb the
radiation for a short while and earth’s surface.
then they reemit the radiation to
the atmosphere – but also to the
earth!
Exemple: sun – earth Light = electromagnetic radiation

If the earth surface had
accounted for all the radiation
that is emitted from our planet
then the temperature here X-ray UV visible NIR mid-IR teraHz
would have been 35 C lower
than what it is today!
200 380 780 2500 25000 nm
Increasing wavelength
4
Light = electromagnetic radiation Our focus: NIR and mid-IR
Increasing energy Increasing energy
X-ray UV visible NIR mid-IR far-IR X-ray UV visible NIR mid-IR far-IR
200 380 780 2500 25000 nm 200 380 780 2500 25000 nm
50000 12820 4000 400 cm-1
Increasing wavelength Increasing wavelength
Let us examine the following

concepts
SPECTROSCOPY Transmittance
Basic concepts Absorbance
part 2 Reflection
Scattering
Polarisation
Transmittance Transmittance
The sample absorbs a fraction of the light The sample absorbs a fraction of the light
Sample Sample
Light Detector Light Detector

100 20
100 photons enter, 20 leave
5
Transmittance, The transmittance, T,
Usually denoted T is defined as
Sample
T = P/P0
Light Detector
P0=100 P=20
P, P0 = power (suitable unit)
In our example Absorbance?
T = 20/100 = 0.2
i.e. 20%
A = log (P0/P)
In our example: Note that
A = log (100/20) = log5 = A = log (P0/P) = - logT
= 0.699
6
Reflection
We can conclude that...
the light can be completely or

partly absorbed by a sample.
The light can also be
reflected.
We get specular reflection when the surface is Scattering

smooth, mirror reflection, i.e. all (almost all) light
energy leaves the surface in a certain direction. Rayleigh scattering occurs when the radiated objects are
Diffuse reflection occurs when the surface is rough. smaller than the wavelength. Objects = dust particles and down in
Light is reflected in all directions. size to molecules. Rayleigh scattering occurs more commonly at
Most surfaces yield a mixture of specular and diffuse short wavelengths in comparison with long wavelengths. Rayleigh
reflection. scattering is the dominating scattering mechanism in the upper
An important parameter is the ratio between the part of the atmosphere. The blue color of the sky is a result of this
phenomenon. When the radiation from the sun passes through
“roughness” and the wavelength of the light. the atmosphere, the short wavelengths (i.e. blue light) in the
If the wavelength is much less than the surface visible spectrum are “scattered” more than the longer
variations or particle size then diffuse reflection wavelengths. At sun rise and sun set the light from the sun has
dominates. to penetrate a longer distance in the atmosphere in comparison
with the situation at daytime. The scattering of the short
wavelengths the increases and we observe light with longer
Exemple, fine grain sand is experienced to be wavelengths.
smooth by microwaves but is experienced as rough
by visible light.
Scattering
Mie scattering occurs when the particles are of the

same size as the wavelength of light. Dust, smoke and
water vapor are common causes to Mie scattering.
Compared with Rayleigh scattering Mie scattering
occurs to a higher degree at long wavelengths. Mie
scattering occurs in the low layers of the atmosphere
where large particles are found and it dominates when
the weather is cloudy.
7
Scattering
Non-selective scattering
Nonselective scattering occurs when the particles
are much larger than the wavelength of the light.
Water drops and large dust particles give rise to this
type of scattering. All wavelengths are “scattered” at
the same degree – this explains the name
nonselective scattering.
White clouds are white since the blue, green and red
light will be scattered at the same degree. The eye
observes blue + green + red light = white light.
Polarisation
The electrical (and magnetical) field strength of an

electromagnetic wave oscillates perpendicularly versus
the travel direction of the wave. In three dimensions
this means that if the wave propagates in the x
direction then the electrical field strength can oscillate
both in y and z directions or vary between these two
directions in an organised or in an unorganised
manner. The electromagnetic wave is said to have
different modes of polarisation.
Polarisation
If we examine the light emitted by an ordinary

tungsten lamp we will find that the electrical field
strength can oscillate in all directions and randomly in
the yz-plane. When there is no defined relationship
between the time and the direction of the electrical
field strength the light is said to be unpolarised. An
unpolarised wave will oscillate in the y and z
directions over time with the same probability.
Consequently, we can assume that 50% of the
intensity of an incoming unpolarised wave falls along
the y axis – the other 50% falls along the z axis (or
direction).

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SPECTROSCOPY Spectroscopy is the science of

Basic concepts spectra, i.e. it involves a measurement

Umeå 2006-04-10 Bo Karlberg

Light = electromagnetic radiation

Frequency = the number of a

Example: Frequency = 2/s (2 Hz)

The wavelength depends on the type of

λ for visible light is in the range 380-780 nm

nm = nanometer, i.e. 10-9 m (one thousandth

What about the wavenumber of light?

In spectroscopy we usually express

• A photon in the IR range

Exemple: sun – earth Exemple: sun – earth

Exemple: sun – earth Exemple: sun – earth

Exemple: sun – earth Light = electromagnetic radiation

Increasing energy Increasing energy

Increasing wavelength Increasing wavelength

Let us examine the following

Light Detector Light Detector

100 photons enter, 20 leave

P, P0 = power (suitable unit)

In our example Absorbance?

In our example: Note that

A = log (100/20) = log5 = A = log (P0/P) = - logT

the light can be completely or

We get specular reflection when the surface is Scattering

Mie scattering occurs when the particles are of the

The electrical (and magnetical) field strength of an

If we examine the light emitted by an ordinary

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