RSC-BTL-946SIAS S 8/7/09 11:45 Page 7

Introduction to
Spectroscopy

What is spectroscopy? What is light?

One of the frustrations of being a chemist is the fact that Light carries energy in the form of tiny particles known as
no matter how hard you stare at your test tube or photons. Each photon has a discrete amount of energy,
round-bottomed flask you can’t actually see the individual called a quantum. Light has wave properties with
molecules you have made! Even though your product characteristic wavelengths and frequency (see the
looks the right colour and seems to give sensible results diagram below).
when you carry out chemical tests, can you be really sure
The energy of the photons is related to the frequency (m)
of its precise structure?
and wavelength (l) of the light through the two equations:
Fortunately, help is at hand. Although you might not be
able to ‘see’ molecules, they do respond when light
E = hm and m = c /l
energy hits them, and if you can observe that response, (where h is Planck's constant and c is the speed of light).
then maybe you can get some information about that Therefore, high energy radiation (light) will have high
molecule. This is where spectroscopy comes in. frequencies and short wavelengths.
Spectroscopy is the study of the way light The range of wavelengths and frequencies in light is
(electromagnetic radiation) and matter interact. known as the electromagnetic spectrum. This spectrum
There are a number of different types of spectroscopic is divided into various regions extending from very short
techniques and the basic principle shared by all is to wavelength, high energy radiation (including gamma rays
shine a beam of a particular electromagnetic radiation and X-rays) to very long wavelength, low energy radiation
onto a sample and observe how it responds to such a (including microwaves and broadcast radio waves).
stimulus; allowing scientists to obtain information about The visible region (white light) only makes up a small part
the structure and properties of matter. of the electromagnetic spectrum considered to be
380-770 nm. [Note that a nanometre is 10-9 metres].

WAVELENGTH
TH(METRES)
(MET

RADIO MICROWAVE INFARED VISIBLE ULTRAVIOLET X-RAY GAMMA RAY

3 -2 -5 -6 -8 -10
10 10 10 5x10
0 10 10 10 -12

MOLECULES

ATOMS

BUTTERFLY

PINHEAD
HUMANS ATOMIC
PROTOZOANS NUCLEUS

INCREASING FREQUENCY m
BUILDINGS

INCREASING WAVELENGTH l INCREASING ENERGY E

10 4 10 8 10 12 10 15 10 16 10 18 10 20

FREQUENCY (HZ)

Copyright © 2009 Royal Society of Chemistry www.rsc.org

RSC-BTL-946SIAS S 8/7/09 11:45 Page 8

SPECTROSCOPY INTRODUCTION 2

When matter absorbs electromagnetic radiation the To ‘see’ a molecule we need to use light having a
change which occurs depends on the type of radiation, wavelength smaller than the molecule itself (approximately
and therefore the amount of energy, being absorbed. 10–10 m). Such radiation is found in the X-ray region of the
Absorption of energy causes an electron or molecule to go electromagnetic spectrum and is used in the field of
from an initial energy state (ground state) to a high energy X-ray crystallography. This technique yields very detailed
state (excited state) which could take the form of the three-dimensional pictures of molecular structures –
increased rotation, vibration or electronic excitation. the only drawback being that it requires high quality
By studying this change in energy state scientists are able crystals of the compound being studied. Although other
to learn more about the physical and chemical properties spectroscopic techniques do not yield a three-dimensional
of the molecules. picture of a molecule they do provide information about its
characteristic features and are therefore used routinely in
• Radio waves can cause nuclei in some atoms to
structural analysis.
change magnetic orientation and this forms the basis
of a technique called nuclear magnetic resonance Mass spectrometry is another useful technique used by
(NMR) spectroscopy. chemists to help them determine the structure of
molecules. Although sometimes referred to as mass
• Molecular rotations are excited by microwaves.
spectroscopy it is, by definition, not a spectroscopic
• Electrons are promoted to higher orbitals by technique as it does not make use of electromagnetic
ultraviolet or visible light. radiation. Instead the molecules are ionised using high
energy electrons and these molecular ions subsequently
• Vibrations of bonds are excited by infrared radiation.
undergo fragmentation. The resulting mass spectrum
The energy states are said to be quantised because a contains the mass of the molecule and its fragments
photon of precise energy and frequency (or wavelength) which allows chemists to piece together its structure.
must be absorbed to excite an electron or molecule from
In all spectroscopic techniques only very small quantities
the ground state to a particular excited state.
(milligrams or less) of sample are required, however, in
Since molecules have a unique set of energy states that mass spectrometry the sample is destroyed in the
depend on their structure, IR, UV-visible and NMR fragmentation process whereas the sample can be
spectroscopy will provide valuable information about the recovered after using IR, UV-visible and NMR
structure of the molecule. spectroscopy.

TECHNIQUE RADIATION WHAT CAN IT SEE?

Nuclear Magnetic Radio waves How neighbouring atoms of

Resonance (NMR) (10-3 m) Electrons flipping magnetic spin certain nuclei (e.g. 1H, 13C,
spectroscopy 19F, 31P) in a molecule are

10-3 m connected together, as well as

how many atoms of these type
are present in different locations
in the molecule.

Infra-red Infra-red 10-5 m NOTE The functional groups which are

spectroscopy (10-5 m) Molecule vibrations present in a molecule.

UV-visible Ultra-violet 10-8 m Conjugated systems (i.e.

spectroscopy (10-8 m) NOTE
alternating single and double
Electrons promoted bonds) in organic molecules as well
to higher energy state as the metal-ligand interactions in
transition metal complexes.

X-ray X-rays How all the atoms in a

crystallography (10-10 m) molecule are connected in a
10-10 m x-ray
three-dimensional arrangement.

+
Mass Non-spectroscopic The mass to charge ratio of the
+
spectrometry technique molecular ion (i.e. the molecular
+ weight) and the fragmentation
pattern which may be related to
Molecules fragment the structure of the molecular ion.

Copyright © 2009 Royal Society of Chemistry www.rsc.org