Spectroscopy: Electromagnetic Radiation
Spectroscopy: Electromagnetic Radiation
Spectroscopy: Electromagnetic Radiation
Electromagnetic radiation:
Electromagnetic radiation (often abbreviated E-M radiation or EMR) is a phenomenon that takes
the form of self-propagating waves in a vacuum or in matter. It comprises electric and magnetic
field components, which oscillate in phase perpendicular to each other and perpendicular to the
direction of energy propagation.
Electromagnetic radiation is classified into several types according to the frequency of its wave;
these types include (in order of increasing frequency and decreasing wavelength): radio waves,
microwaves, infrared radiation, visible light, ultraviolet radiation, X-rays and gamma rays. A
small and somewhat variable window of frequencies is sensed by the eyes of various organisms;
this is what is called the visible spectrum. The photon is the quantum of the electromagnetic
interaction and the basic "unit" of light and all other forms of electromagnetic radiation and is
also the force carrier for the electromagnetic force.
Electromagnetic waves are produced by the motion of electrically charged particles. These waves are also
called "electromagnetic radiation" because they radiate from the electrically charged particles. They travel
through empty space as well as through air and other substances.
Electromagnetic waves were first postulated by James Clerk Maxwell and subsequently
confirmed by Heinrich Hertz. Maxwell derived a wave form of the electric and magnetic
equations, revealing the wave-like nature of electric and magnetic fields, and their symmetry.
Because the speed of EM waves predicted by the wave equation coincided with the measured
speed of light, Maxwell concluded that light itself is an EM wave.
Generally, EM radiation (the designation 'radiation' excludes static electric and magnetic and
near fields) is classified by wavelength into radio, microwave, infrared, the visible region we
perceive as light, ultraviolet, X-rays and gamma rays. Arbitrary electromagnetic waves can
always be expressed by Fourier analysis in terms of sinusoidal monochromatic waves which can
be classified into these regions of the spectrum.
The behavior of EM radiation depends on its wavelength. Higher frequencies have shorter
wavelengths, and lower frequencies have longer wavelengths. When EM radiation interacts with
single atoms and molecules, its behavior depends on the amount of energy per quantum it
carries. Spectroscopy can detect a much wider region of the EM spectrum than the visible range
of 400 nm to 700 nm.
Spectroscopy
Introduction
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic radiation by
matter to qualitatively or quantitatively study the matter or to study physical processes. The
matter can be atoms, molecules, atomic or molecular ions, or solids. The interaction of radiation
with matter can cause redirection of the radiation and/or transitions between the energy levels of
the atoms or molecules.
Absorption:
A transition from a lower level to a higher level with transfer of energy from the radiation field to an
absorber, atom, molecule, or solid.
Matter can capture electromagnetic radiation and convert the energy of a photon to internal
energy. This process is called absorption. Energy is transferred from the radiation field to the
absorbing species. We describe the energy change of the absorber as a transition or an excitation
from a lower energy level to a higher energy level. Since the energy levels of matter are
quantized, only light of energy that can cause transitions from one level to another will be
absorbed.
The type of excitation depends on the wavelength of the light. Electrons are promoted to higher
orbitals by ultraviolet or visible light, vibrations are excited by infrared light, and rotations are
excited by microwaves.
Absorption spectroscopy is one way to study the energy levels of the atoms, molecules, and
solids. An absorption spectrum is the absorption of light as a function of wavelength. The
spectrum of an atom or molecule depends on its energy-level structure, making absorption
spectra useful for identifying compounds.
Emission:
A transition from a higher level to a lower level with transfer of energy from the emitter to the radiation
field. If no radiation is emitted, the transition from higher to lower energy levels is called nonradiative
decay.
Atoms, molecules, or solids that are excited to high energy levels can decay to lower levels by
emitting radiation (emission or luminescence). For atoms excited by a high-temperature energy
source this light emission is commonly called atomic or optical emission (see atomic-emission
spectroscopy) and for atoms excited with light it is called atomic fluorescence (see atomic-
fluorescence spectroscopy). For molecules it is called fluorescence if the transition is between
states of the same spin and phosphorescence if the transition occurs between states of different
spin. Separate documents describe molecular fluorescence, which can be done with compact
instruments, and laser-induced fluorescence.
When electromagnetic radiation passes through matter, most of the radiation continues in its
original direction but a small fraction is scattered in other directions. Light that is scattered at the
same wavelength as the incoming light is called Rayleigh scattering. Light that is scattered in
transparent solids due to vibrations (phonons) is called Brillouin scattering. Brillouin scattering
is typically shifted by 0.1 to 1 cm-1 from the incident light. Light that is scattered due to
vibrations in molecules or optical phonons in solids is called Raman scattering. Raman scattered
light is shifted by as much as 4000 cm-1 from the incident light.
Characteristic of Radiation
Introduction
Many molecules absorb ultraviolet or visible light. The absorbance of a solution increases as
attenuation of the beam increases. Absorbance is directly proportional to the path length, b, and
the concentration, c, of the absorbing species. Beer's Law states that
Different molecules absorb radiation of different wavelengths. An absorption spectrum will show
a number of absorption bands corresponding to structural groups within the molecule. For
example, the absorption that is observed in the UV region for the carbonyl group in acetone is of
the same wavelength as the absorption from the carbonyl group in diethyl ketone.
Electronic transitions
The absorption of UV or visible radiation corresponds to the excitation of outer electrons. There
are three types of electronic transition which can be considered;
When an atom or molecule absorbs energy, electrons are promoted from their ground state to an
excited state. In a molecule, the atoms can rotate and vibrate with respect to each other. These
vibrations and rotations also have discrete energy levels, which can be considered as being
packed on top of each electronic level.
n* Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are capable of
n* transitions. These transitions usually need less energy than * transitions. They can
be initiated by light whose wavelength is in the range 150 - 250 nm. The number of organic
functional groups with n* peaks in the UV region is small.
Molar absorbtivities from n* transitions are relatively low, and range from 10 to100 L mol -1
cm-1 . * transitions normally give molar absorbtivities between 1000 and 10,000 L mol -1
cm-1 .
The solvent in which the absorbing species is dissolved also has an effect on the spectrum of the
species. Peaks resulting from n* transitions are shifted to shorter wavelengths (blue shift)
with increasing solvent polarity. This arises from increased solvation of the lone pair, which
lowers the energy of the n orbital. Often (but not always), the reverse (i.e. red shift) is seen for
* transitions. This is caused by attractive polarisation forces between the solvent and the
absorber, which lower the energy levels of both the excited and unexcited states. This effect is
greater for the excited state, and so the energy difference between the excited and unexcited
states is slightly reduced - resulting in a small red shift. This effect also influences n*
transitions but is overshadowed by the blue shift resulting from solvation of lone pairs.
Many inorganic species show charge-transfer absorption and are called charge-transfer
complexes. For a complex to demonstrate charge-transfer behaviour, one of its components must
have electron donating properties and another component must be able to accept electrons.
Absorption of radiation then involves the transfer of an electron from the donor to an orbital
associated with the acceptor.
Introduction
Luminescence is the emission of light by a substance. It occurs when an electron returns to the
electronic ground state from an excited state and loses it's excess energy as a photon.
The electronic states of most organic molecules can be divided into singlet states and triplet
states;
Chemiluminescence
NO + O3 NO2* + O2
The following graph shows the spectral distribution of radiation emitted by the above reaction:
Theoretical Principles of IR Spectroscopy
Introduction
The term "infra red" covers the range of the electromagnetic spectrum between 0.78 and 1000
m. In the context of infra red spectroscopy, wavelength is measured in "wavenumbers", which
have the units cm-1.
wavenumber = 1 / wavelength in centimeters
It is useful to divide the infra red region into three sections; near, mid and far infra red;
Region Wavelength range (m) Wavenumber range (cm-1)
Near 0.78 - 2.5 12800 - 4000
Middle 2.5 - 50 4000 - 200
Far 50 -1000 200 - 10
The most useful I.R. region lies between 4000 - 670cm-1.
IR radiation does not have enough energy to induce electronic transitions as seen with UV.
Absorption of IR is restricted to compounds with small energy differences in the possible
vibrational and rotational states.
For a molecule to absorb IR, the vibrations or rotations within a molecule must cause a net
change in the dipole moment of the molecule. The alternating electrical field of the radiation
(remember that electromagnetic radation consists of an oscillating electrical field and an
oscillating magnetic field, perpendicular to each other) interacts with fluctuations in the dipole
moment of the molecule. If the frequency of the radiation matches the vibrational frequency of
the molecule then radiation will be absorbed, causing a change in the amplitude of molecular
vibration.
Molecular rotations
Rotational transitions are of little use to the spectroscopist. Rotational levels are quantized, and
absorption of IR by gases yields line spectra. However, in liquids or solids, these lines broaden
into a continuum due to molecular collisions and other interactions.
Molecular vibrations
The positions of atoms in a molecules are not fixed; they are subject to a number of different
vibrations. Vibrations fall into the two main catagories of stretching and bending.
Rocking
Scissoring
Wagging
Twisting
Vibrational coupling
In addition to the vibrations mentioned above, interaction between vibrations can occur
(coupling) if the vibrating bonds are joined to a single, central atom. Vibrational coupling is
influenced by a number of factors;
Strong coupling of stretching vibrations occurs when there is a common atom between
the two vibrating bonds
Coupling of bending vibrations occurs when there is a common bond between vibrating
groups
Coupling between a stretching vibration and a bending vibration occurs if the stretching
bond is one side of an angle varied by bending vibration
Coupling is greatest when the coupled groups have approximately equal energies
No coupling is seen between groups separated by two or more bonds
Instrumentation of UV –Visible Spectroscopy
Introduction
Instruments for measuring the absorption of U.V. or visible radiation are made up of the
following components;
Instrumental components
Sources of UV radiation
It is important that the power of the radiation source does not change abruptly over it's
wavelength range.
Both deuterium and hydrogen lamps emit radiation in the range 160 - 375 nm. Quartz windows
must be used in these lamps, and quartz cuvettes must be used, because glass absorbs radiation of
wavelengths less than 350 nm.
Tungsten/halogen lamps contain a small amount of iodine in a quartz "envelope" which also
contains the tungsten filament. The iodine reacts with gaseous tungsten, formed by sublimation,
producing the volatile compound WI2. When molecules of WI2 hit the filament they decompose,
redepositing tungsten back on the filament. The lifetime of a tungsten/halogen lamp is
approximately double that of an ordinary tungsten filament lamp. Tungsten/halogen lamps are
very efficient, and their output extends well into the ultra-violet. They are used in many modern
spectrophotometers.
An entrance slit
A collimating lens
A dispersing device (usually a prism or a grating)
A focusing lens
An exit slit
Polychromatic radiation (radiation of more than one wavelength) enters the monochromator
through the entrance slit. The beam is collimated, and then strikes the dispersing element at an
angle. The beam is split into its component wavelengths by the grating or prism. By moving the
dispersing element or the exit slit, radiation of only a particular wavelength leaves the
monochromator through the exit slit.
The containers for the sample and reference solution must be transparent to the radiation which
will pass through them. Quartz or fused silica cuvettes are required for spectroscopy in the UV
region. These cells are also transparent in the visible region. Silicate glasses can be used for the
manufacture of cuvettes for use between 350 and 2000 nm.
Detectors
A photon of radiation entering the tube strikes the cathode, causing the emission of several
electrons. These electrons are accelerated towards the first dynode (which is 90V more positive
than the cathode). The electrons strike the first dynode, causing the emission of several electrons
for each incident electron. These electrons are then accelerated towards the second dynode, to
produce more electrons which are accelerated towards dynode three and so on. Eventually, the
electrons are collected at the anode. By this time, each original photon has produced 10 6 - 107
electrons. The resulting current is amplified and measured.
Photomultipliers are very sensitive to UV and visible radiation. They have fast response times.
Intense light damages photomultipliers; they are limited to measuring low power radiation.
A linear photodiode array comprises many small silicon photodiodes formed on a single silicon
chip. There can be between 64 to 4096 sensor elements on a chip, the most common being 1024
photodiodes. For each diode, there is also a storage capacitor and a switch. The individual diode-
capacitor circuits can be sequentially scanned.
In use, the photodiode array is positioned at the focal plane of the monochromator (after the
dispersing element) such that the spectrum falls on the diode array. They are useful for recording
UV-Vis. absorption spectra of samples that are rapidly passing through a sample flow cell, such
as in an HPLC detector.
Charge-Coupled Devices (CCDs) are similar to diode array detectors, but instead of diodes, they
consist of an array of photocapacitors.
Instrumentation of IR Spectroscopy
Introduction
Instrumental components
Sources
An inert solid is electrically heated to a temperature in the range 1500-2000 K. The heated
material will then emit infra red radiation.
The Nernst glower is a cylinder (1-2 mm diameter, approximately 20 mm long) of rare earth
oxides. Platinum wires are sealed to the ends, and a current passed through the cylinder. The
Nernst glower can reach temperatures of 2200 K.
The Globar source is a silicon carbide rod (5mm diameter, 50mm long) which is electrically
heated to about 1500 K. Water cooling of the electrical contacts is needed to prevent arcing. The
spectral output is comparable with the Nernst glower, execept at short wavelengths (less than 5
m) where it's output becomes larger.
The incandescent wire source is a tightly wound coil of nichrome wire, electrically heated to
1100 K. It produces a lower intensity of radiation than the Nernst or Globar sources, but has a
longer working life.
Detectors
There are three catagories of detector;
Thermal
Pyroelectric
Photoconducting
Thermocouples consist of a pair of junctions of different metals; for example, two pieces of
bismuth fused to either end of a piece of antimony. The potential difference (voltage) between
the junctions changes according to the difference in temperature between the junctions
Pyroelectric detectors are made from a single crystalline wafer of a pyroelectric material, such as
triglycerine sulphate. The properties of a pyroelectric material are such that when an electric
field is applied across it, electric polarisation occurs (this happens in any dielectric material). In a
pyroelectric material, when the field is removed, the polarisation persists. The degree of
polarisation is temperature dependant. So, by sandwiching the pyroelectric material between two
electrodes, a temperature dependant capacitor is made. The heating effect of incident IR
radiation causes a change in the capacitance of the material. Pyroelectric detectors have a fast
response time. They are used in most Fourier transform IR instruments.
Photoelectric detectors such as the mercury cadmium telluride detector comprise a film of
semiconducting material deposited on a glass surface, sealed in an evacuated envelope.
Absorption of IR promotes nonconducting valence electrons to a higher, conducting, state. The
electrical resistance of the semiconductor decreases. These detectors have better response
characteristics than pyroelectric detectors and are used in FT-IR instruments - particularly in GC
- FT-IR.
Types of instrument
Radiation from the source is flicked between the reference and sample paths. Often, an optical
null system is used. This is when the detector only responds if the intensity of the two beams is
unequal. If the intensities are unequal, a light attenuator restores equality by moving in or out of
the reference beam. The recording pen is attached to this attenuator.
Fourier-transform spectrometers
Any waveform can be shown in one of two ways; either in frequency domain or time domain.
Dispersive IR instruments operate in the frequency domain. There are, however, advantages to
be gained from measurement in the time domain followed by computer transformation into the
frequency domain.
If we wished to record a trace in the time domain, it could be possible to do so by allowing
radiation to fall on a detector and recording its response over time. In practice, no detector can
respond quickly enough (the radiation has a frequency greater than 1014 Hz). This problem can be
solved by using interference to modulate the i.r. signal at a detectable frequency. The Michelson
interferometer is used to produce a new signal of a much lower frequency which contains the
same information as the original IR signal. The output from the interferometer is an
interferogram.
Radiation leaves the source and is split. Half is reflected to a stationary mirror and then back to
the splitter. This radiation has travelled a fixed distance. The other half of the radiation from the
source passes through the splitter and is reflected back by a movable mirror. Therefore, the path
length of this beam is variable. The two reflected beams recombine at the splitter, and they
interfere (e.g. for any one wavelength, interference will be constructive if the difference in path
lengths is an exact multiple of the wavelength. If the difference in path lengths is half the
wavelength then destructive interference will result). If the movable mirror moves away from the
beam splitter at a constant speed, radiation reaching the detector goes through a steady sequence
of maxima and minima as the interference alternates between constructive and destructive
phases.
The moving mirror must travel smoothly; a frictionless bearing is used with electromagnetic
drive. The position of the mirror is measured by a laser shining on a corner of the mirror. A
simple sine wave interference paatern is produced. Each peak indicates mirror travel of one half
the wavelength of the laser. The accuracy of this measurement system means that the IR
frequency scale is accurate and precise.
In the FT-IR instrument, the sample is placed between the output of the interferometer and the
detector. The sample absorbs radiation of particular wavelengths. Therefore, the interferogram
contains the spectrum of the source minus the spectrum of the sample. An interferogram of a
reference (sample cell and solvent) is needed to obtain the spectrum of the sample.
After an interferogram has been collected, a computer performs a Fast Fourier Transform, which
results in a frequency domain trace (i.e intensity vs. wavenumber) that we all know and love.
The detector used in an FT-IR instrument must respond quickly because intensity changes are
rapid (the moving mirror moves quickly). Pyroelectric detectors or liquid nitrogen cooled photon
detectors must be used. Thermal detectors are too slow.
To acheive a good signal to noise ratio, many interferograms are obtained and then averaged.
This can be done in less time than it would take a dipersive instrument to record one scan.