PHY 454 SPECTROSCOPY 3 Credits

Spontaneous and stimulated emission. Einstein coefficients lifetimes of excited state metastable
state. Lasers and Masers. Fiber Optics. Selection rules (explained in terms of atomic and photon
angular momentum). NMR nuclear properties. Basic NMR spectrometer. Detection of resonance.
Line width, Q - values. ESR, basic spectrometer, resonance. Chemical shifts. Differences between
NMR and ESR. Applications of NMR and ES. Atomic spectra. Electronic, vibrational and
rotational spectra in molecules. IR, visible, UV absorption and emission spectra. Raman effect. X-
ray spectroscopy. Gamma spectroscopy. Mass spectroscopy.

1. Modern Spectroscopy. 4th Ed. Michael Hollas, John Wiley & Sons, New Jessey, 2004.
2. Handbook on Spectroscopy, G. Gauglitz, Wiley-VCH & Co GmBH, Weinheim, 2003.
3. Introduction to Spectroscopy. 4th Ed. Donald L. Pavia, Gary M. Lampman, Brooks/Cole
Cengage Learning, Australia, 2009.

SPECTROSCOPY
Spectroscopy is an experimental subject and is concerned with absorption, emission, scattering of
electromagnetic radiation by an atom or molecule. It has so many applications in physics medicine,
chemistry and engineering.

The basic principle of spectroscopy is matter interacting with radiation and being detected. The
spectra might be modified by changes in the state of the material after radiation. From the spectra
one cannot infer merely the presence of element and compound and something in the mechanism
of atom or molecule which have different spectra.

We will have the opportunity to reveal the methods later.

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ELECTROMAGNETIC RADIATION AND ITS INTERRACTION WITH ATOMS AND
MOLECULES.

Electromagnetic radiation includes light and other radiation of longer and shorter wavelength. As
the name implies it contains both electric and magnetic component which are best illustrated by
considering a plane of linearly or plane polarized radiation shown below. Plane polarized
electromagnetic radiation travelling along the x axis, 𝐸𝑦 and Hz axes.

Fig. 1 Illustrates a photon of such radiation travelling along the x-axis.

The electric component is a form of oscillating electric field of strength E and magnetic field of
strength H. These oscillating fields are right angle to each other. If the direction of the vector E
and H are y and z respectively then,

𝐸𝑦 = 𝐴 sin 2𝜋𝑣𝑡 − 𝑘𝑥

𝐻𝑧 = 𝐴 sin 2𝜋𝑣𝑡 − 𝑘𝑥
The plane of polarization is conventionally taken to be the plane containing the direction E because
the interaction of the electromagnetic with matter is commonly through electric field.

2
From Fig 2, the states m and n of an atom or a molecule are stationary states are so called because
they are time independent Schrödinger equation. The pair of states may be for example electronic,
vibration or rotation. We consider the three processes that may occur when such a two-state system

3
is subjected to radiation of frequency ν and wave number 𝑣̅ corresponding to energy separation
∆E

∆E = En− 𝐸𝑚 = ℎ𝑣

1. INDUCED ABSORPTION

The molecule of an atom absorbs a quantum of radiation and is excited from m to n

𝑀 + ℎ𝑐𝑣̅ → 𝑀∗
This is the familiar absorption process illustrated by the appearance of an aqueous solution of
copper sulphate as blue due to absorption of complementary colour red by the solution.

2. SPONTANEOUS EMISSION

𝑀∗ (in state n) spontaneously emits a quantum of radiation

𝑀∗ = 𝑀 + ℎ𝑐𝑣̅
Almost all emission that we usually encounter such as dust from sodium vapour or tungsten
filament are spontaneous type.

3. INDUCED OR STIMULATED EMISSION

This is a different type of emission process from that of type 2 in that a quantum of radiation of
wave number 𝑣̅ is given to atom or molecule and it is given by the equation

∆𝐸 = 𝐸𝑛 − 𝐸𝑚 = ℎ𝑣 = ℎ𝑐𝑣̅
It is required to be induced or stimulated M* to go from n to m and this process is represented by

𝑀∗ + ℎ𝑐𝑣̅ = 𝑀 + 2ℎ𝑐𝑣̅
The rate of change of population 𝑁𝑛 of state n due to induced absorption is given by
𝑑𝑁𝑛
= 𝑁𝑚 𝐵𝑚𝑛 𝜌(𝑣̅ ) (1)
𝑑𝑡

4
Where 𝐵𝑚𝑛 is Einstein coefficient

𝜌(𝑣̅ ) – the spectral radiation density and is given by

8𝜋ℎ𝑐𝑣̅ 3
𝜌(𝑣̅ ) = ℎ𝑣 (2)
exp( )−1
𝑘𝑇

Similarly, induced emission changes the population of 𝑁𝑛 by

𝑑𝑁𝑛
= −𝑁𝑛 𝐵𝑛𝑚 𝜌(𝑣̅ ) (3)
𝑑𝑡

Where 𝐵𝑛𝑚 is Einstein coefficient for the process and is equal to 𝐵𝑚𝑛 , that is,
𝐵𝑚𝑛
=1 (4)
𝐵𝑛𝑚

For spontaneous emission we have

𝑑 𝑁𝑛
= −𝑁𝑛 𝐴𝑛𝑚
𝑑𝑡

Where 𝐴𝑛𝑚 is Einstein coefficient and the absence of 𝜌(𝑣) indicates spontaneous process.

When a radiation of wave number ̅ 𝑣 is present all the three processes are going on at once and the
populations have reached their equilibrium values.
𝑑 𝑁𝑛
= (𝑁𝑚 − 𝑁𝑛 )𝐵𝑛𝑚 𝜌(𝑣) − 𝑁𝑛 𝐴𝑛𝑚 = 0 (5)
𝑑𝑡

At equilibrium, they are related through Boltzmann’s distribution law given by

𝑁𝑛 𝑔𝑛 −∆𝐸 −∆𝐸
= 𝑒𝑥𝑝 = 𝑒𝑥𝑝 (6)
𝑁𝑚 𝑔𝑚 𝑘𝑇 𝑘𝑇

If the degree of degeneracy 𝑔𝑛 and 𝑔𝑚 states are the same then the n and m are the same and
substituting equation 6 into 2 we have,

𝐴𝑛𝑚 = 8𝜋ℎ𝑐𝑣̅ 3 𝐵𝑛𝑚 (7)

From the above equation, it points out an important fact that spontaneous emission increases
rapidly relative to the induced emission as wavelength 𝑣̅

Since laser operates entirely by induced emission, the equation above is particularly relevant to
laser design.

From equation (7)

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 𝐴𝑛𝑚 ℎ𝑐𝑣̅
= exp( )−1
𝐵𝑛𝑚 𝜌(𝑣̅) 𝑘𝑇

This shows that for atoms in thermal equilibrium with radiation, spontaneous emission is far
greater more probable than stimulated emission if ℎ𝑐𝑣̅ ≫ 𝑘𝑇

Therefore stimulated emission can be ignored in such a transition in electronic transition in both
atoms and molecules.

Stimulated emission can become more significant if ℎ𝑐𝑣̅ ≈ 𝑘𝑇. A condition that applies at room
temperature to atomic transition in the microwave region of electromagnetic spectrum.

Now we will like to understand the operation of lasers and masers.

The ratio of emission rate to absorption rate is given by

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑚𝑖𝑠𝑠𝑖𝑜𝑛 𝑁𝑛 𝑅𝑛−𝑚 𝑁𝑛 𝐴𝑛𝑚 + 𝑁𝑛 𝐵𝑛𝑚 𝜌(𝑣) 𝐴𝑛𝑚 𝑁𝑛

= = = (1 + )
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑁𝑚 𝑅𝑚−𝑛 𝑁𝑛 𝐵𝑚𝑛 𝜌(𝑣) 𝐵𝑛𝑚 𝜌(𝑣) 𝑁𝑚

If 𝐸𝑛 − 𝐸𝑚 ≪ 𝐾𝑇 ,we can ignore the second term in the parenthesis as it is very much smaller than
1 then we obtain

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑚𝑖𝑠𝑠𝑖𝑜𝑛 𝑁𝑛
=
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑁𝑚

We can have in general not assume equilibrium situation. Then in situations of thermal equilibrium
where Boltzmann’s factor applies we expect 𝑁𝑛 < 𝑁𝑚 . But in non equilibrium situations any ratio
is possible.

If we now have a means of inverting the normal population state so that 𝑁𝑛 > 𝑁𝑚 , then the
emission will exceed absorption rate. This means that the applied ratio of wave vector is equal to
𝐸𝑛 −𝐸𝑚
𝑣̅ = will be amplified in intensity by interaction process much more such radiation
ℎ𝑐
emerging than entering.

Of course such a process will reduce the population of the upper state 𝐸𝑛 until equilibrium is
established.

In other to sustain the process we must use such method to maintain the population inversion of
the state. Devices that do this are called Lasers or Masers. Energy must be projected into the system

6
most commonly by optical pumping and the output is an intense coherent monochromatic beam
of radiation.

LASERS

Laser is a device that emits light (electromagnetic radiation) through a process of optical
amplification based the stimulated emission of photons. The term laser is an acronym for Light
Amplification by Stimulated Emission of Radiation

Characteristics of Lasers

1. Monochromatic
2. Coherence
3. Directionality
4. High intensity

Applications of Lasers

Laser is used in several areas such as research, communication, industry, medicine and
environmental care.

Research

Lasers are important tools in physics, chemistry biology and medicine. They are used to register
ultrafast chemical processes as the bonding between atoms to form molecules, to study the process
when cells split, or a virus enters into a cell, manipulation of molecules down to extremely low
temperatures. Transfer of energy as possible to different materials in a short time to obtain different
types of emission.

Medicine

Laser is used in medicine to improve precision work like surgery. Brain surgery is an example of
precise surgery that calls for the surgeon to reach the intended area precisely. To make sure of this,
lasers are used both to measure and to point in the area in question. Birthmarks, warts and
discolouring of the skin can easily be removed with an unfocused laser. The operations are quick
and heal quickly and best of all they are less painful than ordinary surgery performed with a scalpel.

Communication

Laser is used as a light source in fiber optics. It has a greater bandwidth (potential 100,000 times
greater) than an ordinary copper cable. It is insensitive to interference from external electrical and
magnetic fields. Crosstalk (hearing in someone’s phone call) is of rare occurrence.

7
Production of Lasers

𝑀∗ + ℎ𝑐𝑣̅ = 𝑀 + 2ℎ𝑐𝑣̅ (8)

Laser is emitted by the process of stimulated or induced radiation. From the diagram below we
realize that the population of the upper level n of the two level systems Nn and Nm before induced
emission would dominate absorption. There is therefore population inversion. To disturb the
normal Boltzmann distribution in which Nm<Nn requires an input energy as show in Fig. 6 below.
This process by which a population inversion is brought is known as pumping (Optical and
electrical pumping). A system which may be in the gaseous, solid or liquid and in which population
inversion has been created is referred to as an active medium.

According to equation (8) the system is acting as an amplifier of radiation falling on it. The
equation shows that for every photon entering the active medium two photons are emitted from it.

To make an oscillator from amplifier requires the language of electronics and positive feedback.
In lasers this is provided by the active medium being between two mirrors both of them highly
reflecting but one rather less in order to allow some of the stimulated radiation to leak out and
form the laser beam. The region bound by the laser beam is called laser cavity. Various laser
systems are used. An example is shown in the Figure below

Fig. 4 Number of wavelengths between mirrors

𝑛𝜆
The mirror separation d must be an integral number of half-wavelengths apart necessitating
2
extremely accurate alignment where 𝑛, 𝜆 𝑎𝑛𝑑 𝑐 are number of wavelengths, wavelength and speed
of light in air respectively. The resonating frequency is frequency ν of the cavity is given by
𝑛𝑐
𝜈=
2𝑑
The reflecting surfaces of the mirrors are specially coated with alternate layers of high and low
dielectric materials such as TiO2 and SiO2 to give almost total reflection at the specific laser
wavelength

8
 2 3 4

fast fast

3
2
lasing

Pumping Pumping 2
Pumping

lasing
fast

1 1 1
a. Two-level b. Three-level c. Four-level lasing
lasing lasing

Fig. 5 Types of lasing levels

Normal Population Inverted Population

Fig. 6 Types of Population distributions

Lasers are possible because light interacts with electrons. Electrons exist in specific energy levels
or states characteristic of that particular atom or molecule. The electrons in the outer rings are more
energetic than the inner rings. The electrons can be excited into higher energy levels by injection
of energy for example a flash of light. When the electrons drop from a higher energy level to a
lower energy level they give out light. The wavelength of light emitted is related to the amount of
energy released. Depending on the particular lasing material being used, specific wavelengths of

9
light are absorbed (to energize or excite the electrons) and specific wavelengths are emitted (when
electrons fall back to their initial levels).

For a ruby laser, a crystal of ruby is formed into a cylinder. A fully reflecting mirror is placed on
one end and a partially reflecting mirror on the other. A high-intensity lamp is spiraled around a
ruby cylinder to provide a flash of white light that triggers the laser action. The green and blue
wavelengths in the flash excite the electrons in the chromium atoms to a higher energy level. Upon
returning to their normal state the electrons emit their characteristic ruby-red light. The mirrors
reflect some of the light back and forth inside the ruby crystal stimulating other excited chromium
atoms to produce more red light.

Fig. 7 Diagram of ruby laser

FIBRE OPTICS
Light in a glass medium can carry more information over longer distances than electrical signals
can carry in a copper or coaxial medium.

Single and Multimode Fibers

Multimode fiber is the first type of fiber that was made in commercial quantities. It has a larger core than
the single-mode fiber, allowing hundreds of modes of light to propagate through the fiber simultaneously.
Larger core diameter of multiple mode fiber facilitates the use of lower-cost optical transmitters (such as
light emitting diodes).

Single mode fiber on the other hand, has much smaller core that allows only one mode of light at a time to
propagate through the core. Single fibers are designed to maintain spectral integrity of each optical signal
over longer distances, allowing more information to be transmitted.

The tremendous information-carrying capacity and low intrinsic loss have made single-mode fiber the ideal
transmission medium for multimode applications. Single-mode fiber is typically used for longer distance
and higher-bandwidth applications. Multimode fiber is used primarily in systems with short transmission
distance.

10
Optical Fiber sizes

The international standard for outer cladding diameter of most single-mode optical fibers is 125 µm and
250 µm for coating. This standard is important because it ensures compatibility during connectors, splices
and tools used throughout the industry. Standard single-mode fibers are manufactured with small core size,
approximately 8-10 µm in diameter, multimode have core size of 62.5 µm.

Uses of Optic Fiber

See attached copies.

Terminology

Optic fiber is the transparent material along which we can transmit light.

Fiber optics is the system or branch of engineering concerned with using the optic fibers. Optic fiber is
therefore used in fiber optics system.

Fiber is a friendly abbreviation for either, so we could say that fiber is used in fiber system.

Optic Fiber in Communication

The search for material that could carry light led to enormous resources poured into research for material
with sufficient clarity to allow the development of an optic fiber to carry the light over long distances. Early
results were disappointing. The losses were such that the light power was halved every three meters along
the route. The glass used for optic fiber is unbelievably clear. We are used to normal ‘window’ glass looking
clear but it is not even on the same planet when compared with the new silica glass. We could construct a
pane of glass several kilometers thick and still match the clarity of a normal window. If water were this
clear we would be able to see the bottom of the deepest parts of the ocean.

We occasionally use plastic for fiber optic but its losses are still impossibly high for long distance
communication but for short links of a few tens of meters it is satisfactory and simple to use. It is finding
increasing applications in hi-fi systems and in automobile control circuitry.

On the other hand, a fiber optic system using a glass fiber is certainly capable of carrying light over long
distances. By converting an input signal into short flashes of light, the optic fiber is able to carry complex
information over distances of more than a hundred kilometers without additional amplification. This is at
least five times better than copper coaxial cables.

A signal used to vary, or modulate the light output of a suitable source usually a laser or an LED (Light
emitting diode). The flashes of light along the fiber and the far end are converted to an electrical signal by
means of a photo-electric cell. Thus the output signal is recovered as shown in the Figure below.

11
 Electrical to optical

c Speaker
Microphone
S
Optical to
p electrical

S-Sound/voice S

Basics of Optic Fiber

𝑠𝑝𝑒𝑒𝑑 𝑜𝑓 𝑙𝑖𝑔ℎ𝑔𝑡 𝑖𝑛 𝑎𝑖𝑟
Refractive index, 𝑛 =
𝑠𝑝𝑒𝑒𝑑 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 𝑖𝑛 𝑚𝑒𝑑𝑖𝑢𝑚

When light passes through a clear material, it slows down by an amount dependent upon a
property of the material called the refractive index. For most materials we use in optic fiber, the
refractive index is around 1.5

Lower refractive index= higher speed of light and vice versa.

Normal Normal

r Θ2
Lower n2

Higher n1
i
Θ1

I= incident angle

r=refracted angle 12
From Snell’s law

𝑛1 sin 𝜃1 = 𝑛2 sin 𝜃2

From the figure above if 𝑛1 = 1.46, 𝑛2 = 1.51 𝑎𝑛𝑑 𝜃1 = 38 𝑜 . 𝑇ℎ𝑒𝑛 𝜃2 = 39.55 𝑜

Critical angle

i
i c

i<c i=c i>c

Windows

The range of frequencies that are able to be transmitted is called bandwidth. We require wide
bandwidth to send or transmit more complex information. We normally use infrared and visible
light for laser communication but infrared in nearly used for all communications. We shall require

13
wavelength selection since some wavelengths are easier and less expensive to produce than others.
The same applies to the photo-detectors at the receiving end of the system.

Some wavelengths are not desirable for example 1380 nm. The losses at this wavelength are very
high due to water within the glass. It is really surprising that glass is not totally waterproof. Water
in the form of hydroxyl ions is absorbed within the molecular structure and absorbed energy with
a wavelength of 1380 nm.

It makes sense to commercially agree on standard wavelengths to ensure that the equipment from
different manufacturers is compatible. These standard wavelengths are called windows and we
optimize the performance of fibers and light sources so that they perform at their best with one of
these windows (Fig. 2.).

The 1300 nm and 1550 nm windows have much lower losses and are used for long distance
communications. The shorter wavelength window centered around 850 nm has higher losses and
are used for shorter range data transmissions and local area network s (LAN), perhaps up to 10
km. The 850 nm window remains in use because the system is less expensive and easier to install.

14
Propagation of light along the fiber

Critical angle

Fig. 2. A length of optic fiber

Where do the rays go A or B?

At angle less than the critical angle it does go to A but angle greater than the critical angle it goes
to B. The above diagram suggests that a useful transmission system can be built from a simple
length of clear glass. Unfortunately, it is not straightforward, as soon as we touch the fiber, we
transfer some grease from the skin onto its surface. This causes a problem.

The contamination of the surface changes the refractive index of the material surrounding the glass.
It was previously air of refractive index 1 and it is now grease which in common with all other
materials has a refractive index greater than 1.

This will locally increase the critical angle and some of the light will now find itself approaching
the surface at an angle less than the new critical angle. It will then be able to escape (Fig. 2.)

Speck of dirt Light escapes

Light ray

Fig. 2. Any contamination causes power loss

15
Dirt, grease, rain and any contamination will allow leakage of the light. We will not be able to
support the fiber let alone keep it perfectly clean. There is therefore, the need for another glass to
cover the core called the cladding added around the outside during manufacturing. The core and
the cladding form a single solid fiber of glass. To enable the glass to be used industrially, it has a
protective layer added. This is called jacket and the material of choice depends on the use to which
the cable is to be put.

16
17
 A

A—Jacket (A plastic layer for mechanical protection )

B—Cladding (A glass layer to keep the core clean)

C—Core (A glass layer to transmit light)

Jacket

Cladding

Core

62.5 µm

125 µm
2 50 µm

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Note:

 The optic fiber is solid and there is no hole through the middle.
 Buffer and jacket are only for mechanical protection
 The light is transmitted through the core but to a small extent, it travels in the cladding and
so the optical clarity of the cladding is still important.

Getting Light into the Fiber

Getting the light into the fiber

Let assume a fiber system with the following

Core refractive index

19
20
SPLICERS AND CONNECTORS

An optical fiber moves closer to the customer, where cable lengths are shorter and cables have
higher fiber count, the need for joining fibers becomes greater. Splicing and connectorizing play a
critical role both in the cost of installation and in system performance.

The object of splicing and connectorizing is precisely match the core of one optical fiber with that
of another in order to produce a smooth junction through which light signals can continue without
alteration or interruption.

There are two ways that fibers are joined:

1. Splices, which form permanent connections between fibers in the system

2. Connectors, which provide remateable connections, typically at termination points.

Fusion Splicing

Fusion Splicing provides a fast, reliable, low-loss, fiber to fiber connection by creating a
homogenous joint between two fiber ends, typically using an electric arc. Fusion splices provide a
high-quality joint with the lowest loss (in the range of 0.01 dB to 0.10 dB for singe mode fibers)
and a practically nonreflective.

21
Mechanical Splicing

Mechanical splicing is an alternative method of making a permanent connection between fibers.

In the past, the disadvantage of mechanical splicing have been slightly higher losses, less-reliable
performance, and a cost associated with each splice. However, advances in the technology have
significantly improved performance. System operators typically use mechanical splicing for
emergency restoration because it is fast, inexpensive and easy. (Mechanical splice losses typically
range from 0.05-0.2 dB for single mode fiber).

Connectors

Connectors are used in applications where flexibility is required in routing an electrical signal from
lasers to receivers, wherever reconfiguration is necessary, and in terminating cables. The
remateable connections simplify system reconfiguration to meet changing customer requirements.

NUCLEUR MAGNETIC RESONANCE (NMR) OR MAGNETIC RESONANCE

IMAGING

Sub-atomic particles like protons and nucleus can be imagined as spinning on their axis. They
have orbital angular momentum quantum number (l) associated with them. Then the spin will
have (2l+1) possible orientation. Therefore the nucleus of the spin ½ will have two possible
orientations, that is, +1/2 and -1/2. In the absence of an external magnetic field, the orientations
are of equal energy. If an external magnetic field is applied, the energy level splits and each is
given by a magnetic quantum number m.

Ms= -1/2
B

Ms=1/2

The neutrons and protons are also spinning and hence they have the same magnetic field
associated with them given as ……
When there is interaction, there will be radiation and the radiation is always in the microwave
region and they do not cause harm.

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INTERACTION ENERGY (U)
𝑈 = −𝜇𝑍 𝐵
𝑒𝐿
𝜇𝑍 = − 2𝑚𝑧 ,since 𝐿𝑍 = 𝑚𝑙 ħ
𝑒ħml
𝜇𝑍 = 2𝑚
𝑒ħ
𝑈 = 𝑚𝑙 𝜇𝐵 𝐵 since 𝜇𝐵 = 2𝑚

The interaction energy U depends on the value of ml because ml determines the orientation of the
orbital magnetic moment relative to the magnetic fields. Because the values of 𝑚𝑙 range from
−𝑙 to +𝑙 in steps of 1, an energy level with a particular value of the orbital quantum number l
contains (2𝑙 + 1)
Proton is a spinning particle and it experiences a magnetic moment. Like an electron, its
magnetic moment has only 2 possible orientations that are determined in the absence of external
magnetic field. Nuclear spin space can be differentiated from electronic spin space by adapting
nuclear spin quantum number I. For a proton I can take values of-1/2 and 1/2

Nuclear Zeeman Effect

Zeeman found that only certain isotopes give rise to multiple nuclear spin states when an
external magnetic field is applied. This is because only isotopes with an odd number of protons
(odd Z) and/an odd number of neutrons (odd N) possess non-zero nuclear spin

NUCLEAR WITH ZERO SPIN

Even Z and even N have zero nuclear magnetic moment cannot be detected by NRM methods.
This is the reason why the parity (odd or even number) of protons and neutrons are important.
Example:
Nuclear spin I=0, such nuclei are invisible to NRM eg.12C, 16O, 18O

NUCLEAR WITH BOTH Z AND N ODD

Such nuclei must have an odd number of unpaired proton (I=1/2) spin and odd number of
unpaired neutron (I=1/2) spin. So the net magnetic spin must be non-zero integer, i.e., they have
a net nuclear spin of an integer multiple of ½. Such nuclear are detectable by NRM. eg. 2H and
14
N

NUCLEAR WITH EVEN Z AND ODD N OR ODD Z AND EVEN N.

23
 This nuclear must have even number of proton spin (all paired) and odd number of unpaired
neutron spins or vice versa. Therefore, the net magnetic spin is an odd integer multiple of ½ and
this nuclear can be detected by NRM. Eg. 1H (I=1/2), 13C(I=1/2),1H(I=1/2),17O(I=5/2),15N(I=1/2)

Single atomic particles such as proton, electron and neutron can have two magnetic orientation
but a complex nuclei can have 2 or more. The total number (multiplicity) of possible spin states
is determined solely by the value of I and multiplicity is (2𝐼 + 1).
Nuclear I Multiplicity m values
12
C 0 1 0
14
N 1 3 -1,0,1
The states are separated in energy with the largest in (nuclear-spin quantum number) with the
largest value corresponding to the lowest energy. The energy of the I th spin state 𝐸𝑖 is directly
proportional to the value of mi and magnetic field strength BO is given by
𝑚𝑖 ℎ𝛾𝐵𝑜
𝐸𝑖 = − 𝛾 -magnetogyric ratio (depends on type of isotope)
2𝜋
The (-) implies that when m is positive corresponds to lower energy state

∆𝐸 = 𝐸𝑚−(1⁄ ) − 𝐸𝑚+(1⁄
2 2)
1 1
= −((− 2) − (2))𝛾ℏ𝐵0

24
 = 𝛾ℏ𝐵0

Nuclear Magnetic Resonance NMR(Magnetic Resonance Imaging)

Infrared spectroscopy helps us to known functional groups present in a molecule. NMR gives
information about the number of magnetically distinct atoms of the type being studied. Atomic
nuclei have a property called spin.
Spin
The following nuclei have spin and therefore respond to NMR
1 2 13 14 19
1𝐻 , 1𝐻 , 6𝐶 , 7𝑁 𝑎𝑛𝑑 9𝐹
12 16
But 6𝐶 𝑎𝑛𝑑 8𝑂 do not respond to NMR. The property of the nuclei that is used for MRI is
nuclear spin quantum number 𝐼. For each nucleus the number 𝐼 is a physical constant and there
are 2𝐼 + 1 allowed spin states with integral differences from 𝐼 to – 𝐼. The individual spin states
fit into the sequence
+𝐼, (𝐼 − 1), … , (−𝐼 + 1), −𝐼
1
A proton or hydrogen nucleus had nuclear spin quantum number 𝐼 = 2 and has two allowed spin
1 1 1
states (2 (2) + 1 = 2) for it nucleus − 2 𝑎𝑛𝑑 + 2
3
For Chlorine nucleus 𝐼 = 2 and four allowed states
3 3 1 1 3
(2 ( ) + 1 = 4) ; − , − , + , +
2 2 2 2 2
In the absence of an applied magnetic field, all the spin states of a given nucleus are equivalent
energy (degenerate) and in a collection of atoms.

Nuclear magnetic Moments

Spin states are not of equivalent energy in an applied magnetic field because the nucleus is a
charged particle and any moving charge generates a magnetic field of its own. Thus, the nucleus
has a magnetic moment µ generated by its charge and spin. For example a hydrogen nucleus has
1 1
a clockwise (+ 2) and anticlockwise (− 2) spin and the nuclear magnetic moment (𝜇) in two
cases pointing in opposite directions. In an applied magnetic field, all protons have magnetic
moment either aligned with the field or opposed to it as shown below

25
 𝜇

𝜇
1 1
Spin + aligned Spin − 2 opposed Direction of applied
2
field

Two allowed spin states of a proton

As an external field is applied the degenerate spin states split into states of unequal energy as show
below

Energy
1
+
2
Against field
1
−
2

1
+
2
With field

1
No field Applied field Magnetic field −
2
𝐵0

3 3 3
In the case of chlorine nucleus 𝐼 = 2, there are four energy levels shown below. The + 2 and − 2
1 1
spin states are aligned with the field and opposed to the field respectively. The + 2 and − 2 spin
states have intermediate orientations as indicated below.

26
Energy
3
+
2 3
+2
3
−2
−12

+12

+32

No magnetic With magnetic field 𝐵0 3 3

− −2
field 2

Absorption of Energy
The nuclear magnetic resonance phenomenon occurs when the nuclei aligned with the magnetic
field are induced to absorb energy and change their spin orientation with respect to the applied
field as shown for a hydrogen nucleus below:

−2
1 +ℎ𝜈

1
+2
Magnetic field
direction

The energy absorbed is a quantized process and the energy absorbed must be equal to the energy
difference between the two states involved
𝐸𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = 𝐸−1 − 𝐸+1 = ℎ𝜈
2 2
The energy difference is a function of the applied field 𝐵0 as shown below

27
 Energy

∆𝐸 = 𝑘𝐵0 = ℎ𝜈

Increasing magnetic field

The stronger the applied field the greater the energy difference between the possible spin states
∆𝐸 = 𝑓(𝐵0 ) 1
The magnitude of the energy level separation depends on the particular nuclei involved. Each
nuclei (hydrogen, chlorine and so on) has a different ratio of magnetic moment to angular
momentum since it has different charge to mass ratio. The ratio is called magnetogyric ratio 𝛾 and
it is a constant for each nuclei and it determines the energy dependence on the magnetic field.
∆𝐸 = 𝑓(𝛾𝐵0 ) = ℎ𝜈 2
ℎ
Since angular momentum is quantized in units of 2𝜋, the final equation takes the form
ℎ
∆𝐸 = 𝛾 ( ) 𝐵0 = ℎ𝜈 3
2𝜋
𝛾
∴ 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝜈 = ( )𝐵0 4
2𝜋
If 𝛾 for a proton is substituted, the unshielded proton should absorb radiation of frequency
42.6 𝑀𝐻𝑧 in a field of 1 Tesla (10000 Gauss or radiation of 60.0 𝑀𝐻𝑧 in a field of 1.41 Tesla
(14,100 Gauss)
Isotope Field Strength Frequency Magnetogyric
(B0) (MHz) Ratio (𝛾)
1 1.00 42.6 267.53
𝐻
1.41 60.0
2 1.00 65.00 41.1
𝐻
13 1.00 10.7 67.28
𝐶
1.41 15.1
19 1.00 40.00 251.7
𝐹
21 1.00 17.2 108.3
𝑃

28
THE MECHANISM OF ABSORBTION (RESONANCE)
The nature of nuclear spin transition can be understood from the analogy of a child’s spinning top.
Protons absorb energy because they begin to precess in the magnetic field. This precession is
similar to that of a spinning top. A spinning nucleus behaves in a similar way under the influence
of an applied magnetic field.
When the magnetic field is applied the nucleus begins to precess about its own axis of spin with
angular frequency 𝜔, which is sometimes called the Larmor frequency. The frequency is directly
proportional to the strengthen of the magnetic field, the stronger the field the higher the rate
(angular frequency,𝜔) of precession. Since the nucleus has a charge, the precession generates an
oscillating electric field of the same frequency. If radio frequency waves of this frequency are
supplied to the precessing proton, the energy can be absorbed. That is, when the frequency of
oscillating electric field component generated by the precessing nucleus, the two fields can couple
and the energy can be transformed from incoming radiation to the nucleus, thus causing spin
change. This condition is called resonance, the nucleus is said to be resonating with incoming
electromagnetic wave.

THE NRM MAGNET

The basic component of NMR spectrometer are magnets to generate the B0 and radio frequency
oscillator to generate B1 in the transmitter coil, the receiver coil to pick up the signal, the
electronics (a computer and the plotter to turn the signal into spectrum and of course a sample to
be analyzed).
Important characteristics of the magnets in any NMR spectrometer are the strength, the stability
and homogeneity of its magnetic field. Not only is the precessional or resonance frequency of
identical nuclei is directly proportional to the strength of B0 but also the difference in
precessional frequency ∆𝑣 of non-identical nuclei.
(𝛾1 −𝛿𝛾2 )
∆𝑣 = 𝑣1-𝑣2= ℎ𝐵0
2𝜋

Therefore there is an advantage to use the strongest available magnet to obtain the greatest
separation and (resolution) between MRM signal.
Types of magnets are permanent magnets, electromagnets and superconducting magnets.

29
PERMANENT MAGNETS
They are less costly, relatively stable. Fixed magnetic field and require current to generate them.
The magnetic fields are very limited approximately 1.4 T
ELECTROMAGNETS
They are huge and more costly to build and operate but their field strength range up (strongest 34
T). The disadvantage is that their electrical resistance is too high in order to generate high current
which are necessary to generate high magnetic fields. This would generate considerable heat.
SUPERCONDUCTING MAGNETS
They are used in NMR spectrometer. They generate field of strength 6-18 T.

LINE WIDTH

The half-width (𝑣1/2) of NMR signals is the width (in Hertz) of the peak at half height
1
𝜈1⁄2 =
𝑇
where T is the relaxation time.

30
Half-width of a spectroscopic signal is inversely proportional to lifetime (relaxation time) of the
species given rise to the signal. Nuclei that are slow to relax (small T values) give broad signals.
The half-width is therefore controlled by the fastest/ (slowest) time of relaxation.

Magnetic Resonance Imaging (MRI)

The production of useful medical images is now called Magnetic Resonance Imaging (MRI). The
element that is normally used is hydrogen since it is the commonest element in the human body
and gives the strongest NMR signal. The experimental set up is shown below.

The Figure above shows the MRI imaging set up

The large coils set up the magnetic field and the RF coils produce the RF pulse of electromagnetic
waves (photons) that cause nuclei to jump from lower to the upper state. The same coils or another
∆𝐸
coil can detect absorption of energy or emitted radiation (𝑓 = ) when the nuclei jumps back to
ℎ
the lower state.

31
The formation of a two-dimensional or a three-dimensional image can be done using a technique
similar to those for computed tomography.
What is measured is for creating an image is the intensity of the absorbed and/or reemitted radiation
from many parts of the body and this would be a measure of the density of H atoms. If the field
gradient is applied after the RF pulse, the frequency of the emitted photons will be a measure of
where they are emitted. If a magnetic field gradient in one direction is applied during excitation
(absorption of photons) and photons of a single frequency are transmitted, only H nuclei in one
thin slice will be excited. By applying a gradient during reemission in a direction perpendicular to
the first, frequency of reemitted radiation will represent depth in that slice. Other ways of varying
the magnetic field throughout the volume of the body can be used in order to correlate NMR
frequency with position.

32
ELECTRON SPIN RESONANCE

It is a branch of absorption spectroscopy in which a radiation having a frequency in microwave

region is absorbed by paramagnetic substances to induce transition between magnetic energy level
of electron with unpaired spin. This means that without unpaired electron, there will not be any
electron resonance. Not all materials show electron spin resonance.
 atoms having an odd number of electrons
 ions having partly filled inner electron shell
 free radicals having unpaired electrons.

BASIC PRINCIPLES OF EPR (ELECTRON PARAMAGNETIC RESONANCE)

hν

𝐵=0 𝐵≠0

In the diagram above, when there is no magnetic field (B=0), the electrons are occupying the same
spin state (it brings degeneracy). But when a static magnetic field is applied the spin states are split
into two (ie ms=+1/2 and ms=-1/2). The ms=-1/2 is parallel to the field. For an electron the energy
of ms equal +1/2 is higher than ms=-1/2.
When a microwave of energy is applied under the magnetic field some of the unpaired electrons
are excited to a higher energy state by an absorption of a photon. The excited electron (s) changes
its direction of spin and relaxes into the ground state by emitting a photon. Microwave absorption
is measured as a function of the magnetic field by electron spin resonance spectroscopy. The higher
the magnetic field, the higher the splitting of the energy levels.

OPERATION OF ESR (ELECTRON SPIN RESONANCE)

A molecule or an atom has discrete or separate states each with a corresponding energy. The main
function of ESR is to measure and interpret the difference in these energies. The difference in
energy is given by h𝑣 where h=planks constant and 𝑣 is the frequency. When an electron absorbs
Electromagnetic energy, there is a transition. When we consider a single electron the degenerate
energy states (the 2 spin states) of the electron have the same energy in the absence of a magnetic
field. When a magnetic field is applied, the spin states diverge and is proportional to the applied

33
magnetic field. Therefore there is no energy difference to measure without a magnetic field. The
energy difference studied in EPR spectroscopy are due to the interaction of unpaired electrons in
the sample with an external magnetic field by EPR spectrometer. This splitting (effects) is called
Zeeman Effect.
We know that an electron is a charged particle and as a result possesses a magnetic moment. It can
also act as a bar magnetic due to its charge and spin and can therefore interact with an external
magnetic field. In the absence of a magnetic field, the magnetic moment of an electron has
randomized direction but in the presence of a magnetic field individual magnetic moment arising
from electron spin of the unpaired electron can be oriented in two directions. The state of lowest
energy will correspond to magnetic moment of electron (µ) aligned along the field (i.e. parallel)
and the state with highest energy when µ is aligned against the magnetic field (anti parallel)

The energy E of the states is given by

1
𝐸 = 𝑔𝜇𝐵 𝐵𝑚𝑠 = ±2𝑔𝜇𝐵 𝐵
The change in energy ∆𝐸 of the two states is given by
∆𝐸 = 12𝑔𝜇𝐵 𝐵 − (−12𝑔𝜇𝐵 𝐵) = 𝑔𝜇𝐵 𝐵
Therefore, the equation describing the absorption or emission of a microwave energy between two
spin states is
∆𝐸 = ℎ𝜈 = 𝑔𝜇𝐵 𝐵
∆𝐸 𝑖𝑠 the energy difference the spin states 𝑚𝑠 = +12 𝑎𝑛𝑑 𝑚𝑠 = −12
ℎ is Planck’s constant
ν is microwave frequency

34
𝑔 is the proportionality factor which is a function of electron’s environment (free electron value is
2.0023 but it is not constant)

RELAXATION is important in other to maintain steady state condition. Electrons that have been
excited to a higher energy level can lose energy and return to a lower energy level.

SATURATION occurs in absence of relaxation. When there is a continuous absorption of energy

by electron in the lower state which leads to equal population in such states (lower and higher
states) ie saturation condition. The ratio of the number of electrons in the upper energy to those in
𝑛1 ∆𝐸
lower energy level is given by Boltzmann’s law = exp(− ).
𝑛2 𝑘𝑇

FREQUENCY RANGES
A magnetic field of 0.35T is often selected for commercial spectrometers. The corresponding
frequency is 9 or 9.5 MHz. Such spectrometers are referred to as X-bands. Some commercial
spectrometers (K-bands) and Q band operates at a higher magnitude field (0.8 or 1.25 T)
respectively. With the corresponding higher microwave frequency of 24 GHZ and 35-36 GHZ
respectively
.

The sample is placed in a sample cavity so that the microwave magnetic field can influence the
sample as shown in the above diagram. The cavity is also situated between the poles of an
electromagnet such that the sample is at the centre of magnetic field induction. The sample is

35
normally placed in a thin walled quartz tube free of paramagnetic impurities. The radiation which
is transmitted by the cavity can be modified by the resonance absorption. The microwave power
transmitted by the cavity is then detected in a rectifier crystal (a semiconducting crystal detector)
is usually used for this purpose. The signal is appropriately amplified and fed into a suitable
recorder.
APPLICATION OF ESR
ESR is used in various branches of science such as chemistry and physics for the detection and
identification of free radicals. ESR is a sensitive method for studying both radicals formed in
chemical reaction themselves. For example when frozen water is decomposed by exposure to high
energy radiation, radicals such as H+ and OH- and H2O are produced. Such radicals can be
identified and studied by EPR. Medical and biological application of ESR also exists. Radicals are
also very reactive and so do not normally occur in high concentrations. Special reagents have been
developed to spin-label molecules of interest. These reagents are particularly useful in biological
systems. Specially designed non-reactive molecules can be attached to specific sites in biological
cell and EPR can then give information on the environment of these so-called spin-labels or spin
probes.

36
MASS SPECTROSCOPY
It is an analytical technique for the determination of the elemental composition of a sample or a
molecule. It is used to explain the chemical structures of molecules such as peptides and other
chemical compounds. The main composition of a mass spectrometer is shown in the diagram
below.

Fig. 1 Processes for mass spectrometer.

The basic principle of the mass spectrometer is to ionize chemical compounds to generate
charged molecules of fragments and measurement of mass-charge ratio. The main procedures
are;
1. A sample is placed in a mass spectrometer and it is vaporized.
2. The component of the sample are ionized by one of a variety of methods (electron
beam) which results in the formation of positively charged particles (ions)
3. The positive ions are then accelerated by an electric field.
4. The computation of the mass to change ratio (m/e) of the particles raise from the details
of motion of the ions as they pass through the magnetic field.
5. Detection of ions which are sorted in the above steps according to mass to charge.
The output of a mass spectrometer shows a plot of relative intensity versus mass to charge ratio.
The most intense peak in the spectrum is termed as the base peak and all the others are reported
relative to its intensity (i.e. base peak intensity). The peaks are typically very sharp and are simply

37
represented as vertical lines. The highest molecules weight peak observed in a spectrum will
typically represent the parent molecule. Generally small peaks are also observed on the left and on
the right of the base peak and the calculated molecular height due to natural isotopic abundance
are normally found on the right of the highest intensity.
APPLICATIONS
1. Identifying unknown compounds by the mass of the compound molecules or their
fragments.
2. To determine the isotopic composition of elements in a compound.
3. Determine the structure of a compound by observing its fragmentations.
4. Determine other physical, chemical or even biological properties of compounds with a
variety of other approaches.

Fig. 2 Schematic Diagram showing mass spectrometer (Courtesy Giancoli 4th Ed)

38
Mass Spectrometer Calculations

The force due to magnetic field is given by

𝐹 = 𝑒𝑣𝐵 1

𝑒 is the charge on electron

𝑣 is the velocity

𝐵 is the magnetic field intensity

In the presence of an electric field, the ions are bent in a curved path so we have

𝐹 = 𝑚𝑎 2

For a circular motion

𝑣2
𝑒𝑣𝐵 = 𝑚 3
𝑟
And thus
𝑒 𝑣
= 4
𝑚 𝐵𝑟
𝑟 is the radius of curvature which can be measured and B is already known. But

𝑒𝐸 = 𝐹

For no deflection, the two forces balance

𝑒𝐸 = 𝑒𝑣𝐵 5
𝐸
𝑣= 6
𝐵
Substituting equation 6 into equation 4, we have
𝑒 𝐸
= 2
𝑚 𝐵 𝑟
Which is equal to

39
 𝑚 𝐵2 𝑟
= 7
𝑒 𝐸
Since the all the parameters on the right are known the mass to charge ratio can be
determined and this ratio is constant for a particular sample.

100%
43

58

50%
71
114

m/e

40
Questions

In a mass spectrometer, germanium atoms have radii of curvature equal to 21.0, 21.6,
21.9, 22.2 and 22.8 cm. The largest radius corresponds to an atomic mass unit of 76
u. What are the atomic masses of other isotopes?

Solution

From equation 7 above, i.e

𝑚 𝐵2 𝑟
=
𝑒 𝐸
Mass m is proportional to r when other parameters are constant. If

22.8 𝑐𝑚 = 76 𝑢
21.0
∴ 21.0 𝑐𝑚 = × 76 𝑢 = 70.0 𝑢
22.8
Similarly, the rest can be calculated

21.6 𝑐𝑚 = 72.0 𝑢

21.9 𝑐𝑚 = 73.0 𝑢

41
 22.2 𝑐𝑚 = 74.0 𝑢

Question 2

A spectrometer is being used to monitor air pollutants. It is difficult however, to

separate molecules with nearly equal masses such as CO (28.0106 u) and N2
(28.0134 u). How large a radius of curvature must a spectrometer have if these two
molecules are to be separated at the film or detector by 0.65 mm. Assume that they
have equal charges.

Solution

𝑞𝐸 = 𝑞𝑣𝐵
𝐸
𝑣=
𝐵

′
𝑚𝑣 2
𝑞𝑣𝐵 =
𝑟
𝑞𝐵′ 𝑟
𝑚=
𝑣
Substituting
𝐸
𝑣=
𝐵
Into m above we have
𝑞𝐵𝐵′ 𝑟
𝑚=
𝐸
Since all the parameters on the right hand side of the equation is known except r and
m is proportional to r, we can write
𝑚𝑐𝑜 𝑟𝑐𝑜
=
𝑚𝑁2 𝑟𝑁2

28.0106 𝑟𝑐𝑜
=
28.0134 𝑟𝑐𝑜 + 0.65

42
 28.0106𝑟𝑐𝑜 + 18.20689 = 28.0134𝑟𝑐𝑜

18.20689 = 0.0028𝑟𝑐𝑜
18.20689
𝑟𝑐𝑜 =
0.0028
= 6502.46

∴ 𝑟𝑁2 = 6502.46 + 0.65

𝑟𝑁2 = 6503.11 𝑚𝑚

Question 3

Carbon atoms of atomic mass 12.0 u are found to be mixed with another unknown
element. In a mass spectrometer with a fixed 𝐵′ , the carbon travels a path of radius
22.4 cm and the unknown element’s path has 26.2 cm radius. What is the unknown
element? Assume that the ions of both elements have the same charge.

Solution
𝑚𝑥 𝑞𝐵𝐵′ 𝑟𝑥 ⁄𝐸 26.2
= = = 1.17
𝑚𝑐 𝑞𝐵𝐵′ 𝑟𝑐 ⁄𝐸 22.4

∴ 𝑚𝑥 = 1.17 × 12.0 𝑢 = 14.0 𝑢

The other element is probably Nitrogen.

43
Atomic Spectroscopy

Atomic Absorption and Emission Spectra

Atoms can absorb and emit packets of electromagnetic radiation having discrete energies
dictated by the detailed atomic structure of the atoms. When the corresponding light is passed
through a prism or spectrograph it is separated spatially according to wavelength, as illustrated in
the following image.

Separation of light by a prism according to wavelength

Continuous Spectrum (Continuum), Emission, and Absorption Spectra

The corresponding spectrum may exhibit a continuum, or may have superposed on the
continuum bright lines (an emission spectrum) or dark lines (an absorption spectrum), as
illustrated in the following figure.

44
 Continuous, emission, and absorption spectra

Origin of Continuum, Emission, and Absorption Spectra

The origins of these three types of spectra are illustrated in the following figure.

Sources of continuous, emission, and absorption spectra

45
Thus, emission spectra are produced by thin gases in which the atoms do not experience many
collisions (because of the low density). The emission lines correspond to photons of discrete
energies that are emitted when excited atomic states in the gas make transitions back to lower-
lying levels.

A continuum spectrum results when the gas pressures are higher. Generally, solids, liquids, or
dense gases emit light at all wavelengths when heated.

An absorption spectrum occurs when light passes through a cold, dilute gas and atoms in the gas
absorb at characteristic frequencies; since the re-emitted light is unlikely to be emitted in the
same direction as the absorbed photon, this gives rise to dark lines (absence of light) in the
spectrum.

Hydrogen Emission and Absorption Series

The spectrum of hydrogen is

particularly important in astronomy
because most of the Universe is
made of hydrogen. Emission or
absorption processes in hydrogen
give rise to series, which are
sequences of lines corresponding to
atomic transitions, each ending or
beginning with the same atomic
state in hydrogen. Thus, for
example, the Balmer Series
involves transitions starting (for
absorption) or ending (for
emission) with the first excited
state of hydrogen, while the Lyman
Series involves transitions that start
or end with the ground state of
hydrogen; the adjacent image Hydrogen emission series
illustrates the atomic transitions
that produce these two series in emission.

46
Because of the details of hydrogen's atomic structure, the Balmer Series is in the visible
spectrum and the Lyman Series is in the the UV. The following image illustrates some of
the transitions in the Balmer series.

The Balmer spectrum of hydrogen

Principle of Absorption Spectroscopy

If the number of molecules is large, the greater the extent of absorption of light of a given
wavelength. Furthermore, the more effective a molecule absorbs light of a given wavelength, the
greater the extent of light of absorption. From the above statement, the empirical formula by Beer
and Lambert known as Beer-Lambert law is formulated

𝐼0 𝐼
𝐴 = log ( ) 𝑜𝑟 − 𝑙𝑜𝑔
𝐼 𝐼0

𝐼0
= log( ) = 𝜀𝑐𝑙
𝐼
For a given wavelength

𝐴 is the absorbance

𝐼0 is the intensity of light incident on upon the sample

𝐼 is the intensity of light leaving the sample

𝑐 is the molar concentration of solute

47
𝑙 is the length

𝜀 is the molar absorptivity

Instrumentation

A typical ultraviolet-visible spectrophotometer consists of light source, a monochromator and a

detector. The light source is usually deuterium lamp (emits radiation of UV spectrum and tungsten
emits visible spectrum. The monochromator is a diffracting grating, its role is to spread the beam
of light into the component wavelengths. The light that passes through the sample of initial
intensity 𝐼0 reaches the detector which records the intensity of the transmitted light 𝐼. The detector
is generally a photomultiplier tube and in modern instruments photodiodes are used.

In thin film technology for photovoltaic applications we use the equation

𝐼
𝐴 = −𝑙𝑜𝑔 1
𝐼0

But from the Tauc relation

𝑛
𝛼ℎ𝜈 = [𝑘(𝐸𝑔 − ℎ𝜈)] 2 2

Where

𝛼 is the absorption coefficient

ℎ𝑐
ℎ𝜈 is the photon energy ( 𝜆 )

𝐸𝑔 is the band gap

k is a constant

𝑛 = 2, 3 is the direct or indirect transition respectively

For a direct transition n=1 and equation 2 becomes

1
𝛼ℎ𝜈 = (𝐸𝑔 − ℎ𝜈)2 3

Squaring both side of the above equation we have

(𝛼ℎ𝜈)2 = 𝑘(𝐸𝑔 − ℎ𝜈)

Therefore, the band gap of the film is determined

48
How do we determine 𝛼?

2.303𝐴
𝛼=
𝑡
𝐴 and 𝑡 are absorbance and thickness of film respectively
𝑚𝑎𝑠𝑠 𝑚2 −𝑚1
Density 𝜌 = 𝑣𝑜𝑙𝑢𝑚𝑒 = 𝑙×𝑏×𝑡

Where 𝑚1 , 𝑚2 are mass of slide with film and mass of slide without film respectively.

𝑙 and 𝑏 are the length and breadth of the film respectively. With the density 𝜌 known the thickness
𝑡 can be determined.

In other to avoid thickness measurement which is requires an accurate measurement we use the
Stern relation which is given by
𝑛
𝐴ℎ𝜈 = [𝑘(ℎ𝜈 − 𝐸𝑔 )] 2

𝑛 = 1 for direct transition and 𝑛 = 4 for indirect transition.

A plot of (𝐴ℎ𝜈)2 against ℎ𝜈 gives a curve and the linear portion extrapolated to the gives the band
gap.

The band gap of thin films can also be determined from the equation (This is not absorption)
𝐸𝑔
𝜌 = 𝜌0 𝑒 2𝑘𝑇

Taking natural logarithm on both sides

𝐸𝑔
𝑙𝑛𝜌 = 𝑙𝑛𝜌0 +
2𝑘𝑇

49
 1 𝐸𝑔
A plot of 𝑙𝑛 𝜌 against 𝑇 gives a straight line of gradient equal to 2𝑘. 𝐸𝑔 can be determined.

Where 𝜌 is the resistivity, 𝑇 is the absolute temperature and 𝑘 is the Boltzmann’s constant
𝑙𝑛⁡ρ

𝐸
gradient = 2𝑘𝑔

𝑘 = 1.38 × 10−23 𝐽𝐾 −1

1 −1
/𝐾
𝑇

50
 10

7
(Ahν) 2/ (eV)2

1
1.1 1.3 1.5 1.7 1.9 2.1
hν/ eV
The Figure above shows a plot (𝐴ℎ𝜈)2 against ℎ𝜈

51
 INFRARED SPECTROSCOPY
Infrared spectroscopy is one of the most important analytical techniques available to today’s
scientists. One of the great advantages of infrared spectroscopy is that samples of any state can be
studied. Exams liquids, solutions, pastes, powders, films, fire gases and surface can be examined
with right choice of sampling technique.

Infrared spectroscopy has been used since 1940’s. The most significant advances in infrared
spectroscopy has come about as a result of the introduction of Fourier-transform spectrometers.
This type of instrument employs an interferometer and exploits the well-established mathematical
process of Fourier-transform. Fourier-transform infrared (FTIR) spectroscopy has dramatically
improved the quality of infrared spectra and minimize the time to obtain data.

Infrared spectroscopy is a technique that is based on the vibration of the atoms of a molecule. An
infrared spectrum is commonly obtained by passing infrared radiation through a sample and
determining what function of the incident radiation is absorbed at a particular energy. The energy
at which any peak in an absorption spectrum appears to correspond to the frequency of vibration
of a part of sample molecule is quantized. The EM radiation absorbed has energy exactly equal to
the energy difference between the excited and ground state.

Region of spectrum Energy Transition

x-ray Band breaking
Ultraviolet/visible Electronic
Infrared Vibrational
microwave Rotational
Radiofrequencies Nuclear spin (nuclear magnetic resonance)
electron spin

Radiation in the infrared range corresponds to the range encompassing the stretching and bending
vibrational frequency of the bonds in most covalent molecules. In the absorption process, these
frequencies of infrared radiation that match the natural vibrational frequencies of the molecule in
question are absorbed, and the energy absorbed serves to increase the amplitude of the vibrational
motions of the bond in the molecules.

NOTE: No all bonds in a molecule are capable of absorbing infrared energy, even if the frequency
of the radiation exactly matches that of the bond motion. Only those bond that have a dipole
moment that changes as a function of time are capable of absorbing infrared radiations. Symmetric
bonds such as those of H2 and Cl2 do not absorb infrared radiations. A bond must present an
electrical dipole that is changing at the same frequency as incoming radiation for energy to be
transferred.

52
USES OF INFRARED SPECTRUM
Every type of bond has a different natural frequency of vibration and since two of the same type
of bond in two different compounds are in two slightly different environment, no two molecules
of different structure have exactly the same infrared absorption pattern or infrared spectrum.
Although, some of the frequencies absorbed in the two cases might be the same in no case of two
different molecules will have their infrared spectra (the patterns of absorption) be identical, thus,
the infrared spectrum can be used for molecules much as a fingerprint can be used for humans. By
comparing the infrared spectra of the substance thought to be identical you can establish whether
they are in fact identical. If their infrared spectra coincides peak for peak (absorption for
absorption) in most cases the two substances will be identical.

STRETCHING AND BENDING

The simplest types or modes of vibrational motion in a molecule that are infrared active and give
rise to infrared absorptions are stretching and bending.

The stretching and bending occur at a particular wave numbers. Examples methyl group give rise
to a symmetric stretching vibration at about 2872cm-1 and a symmetric stretching at 2962cm-1.

53
BOND PROPERTIES AND ABSORPTION TRENDS
Bond strength and the masses of the bonded atoms affect infrared absorption frequency. For the
sake of simplicity, we would restrict our discussion to heteronuclear diatomic molecule (two
different atoms) and its stretching. A diatomic molecule can be considered as two vibrating masses
connected by string. The bond distance continually and periodically changing from kinetic to
potential energy and back again. The total amount of energy is proportional to the frequency of
vibration.
Eosc ∝ ћ𝛖osc which for a harmonic oscillator is determined by the force constant k of the spring or
its stiffness and the masses (m1 and m2) of the two bonded atoms. The natural frequency of the
1 𝑘
vibrating of a bond is given by the equation 𝜐̅ = 2𝜋𝑐 √𝜇 which is derived from Hooke’s law for
vibrating spring. The reduced mass μ of the system is given by:
𝑚1 𝑚2
𝜇=
𝑚1 + 𝑚2

K is a constant that varies from one bond to another.

54
As first approximation, the force constants for triple bonds are three times those of single bonds.
Two things should be noted here, one thing is that, stronger bonds have a large force constant k
and vibrate at higher frequencies than weaker bonds. The second is that bonds between atoms of
higher masses (larger reduced mass, μ) vibrate at lower frequencies than bonds between higher
atoms.

In general, triple bonds are stronger than double bonds and single bonds between the same two
atoms and have higher frequencies of vibration (higher wave numbers).

𝐶 ≡ 𝐶 (2150cm-1) 𝐶 = 𝐶 (1650cm-1) 𝐶 − 𝐶 (1200cm-1)

←increasing K

THE INFRARED SPECTROMETER

The instrument that determines the absorption spectrum of a compound is called infrared
spectrometers. There are two types of infrared spectrometers. They are dispersive and Fourier
transform (FT) instruments. Both work in the range 4000-400cm-1. Though they provide the same
infrared spectrum, the FT infrared spectrometer provide infrared spectrum much faster than
dispersive.
Dispersive Infrared spectrometer.

55
The diagram of this infrared spectrometer is shown above (Courtesy Pavia). The instrument
produces a beam of infrared radiation from hot wire and by means of mirrors, divides it into two
parallel beams of equal-intensity radiation. The sample is placed in one beam and the other beam
is used as a reference. The beam then pass into the monochromator, which disperses each into a
continuous spectrum of frequencies of infrared light. The monochromes consist of a rapidly
rotating sector (beam chopper) that passes the two beams alternatively to a diffracting rating. The
slowly rotating diffracting grating varies the frequency or wavelength of radiation reaching the
thermocouple. The detector senses the ratio between the intensity of the reference and sample
beams. The detector determines the frequencies that have been absorbed and those that are not,
after passing through the sample. Dispersive instruments record the spectrum in the frequency
domain.

56
% transmittance = 𝐼⁄𝐼 𝑥100 I- intensity of sample beam
0

I0- intensity of reference beam

In many parts of the spectrum, the transmittance is nearly 100%, meaning that, the sample is nearly
transparent to radiation of that frequency (does not absorb it). Maximum absorption is thus
represented by a minimum on the chart. The absorption is traditionally called a peak.

FOURIER TRANSFORM SPECTROMETER

A schematic diagram of the FT-IR is shown above. The FT-IR uses an interferometer to process
the energy sent to the sample. In the interferometer, the source energy passes through a beam
splitter, a mirror placed at 450 angle to the incoming radiation which allows the incoming radiation
to pass through but separate it into two perpendicular beams, one undeflected, the other oriented
at 900 angle. The oriented 900 beam in figure goes to a stationary or fixed mirror and in return to
the beam splitter. The undeflected beam goes to the moving mirror and it also returned to the beam
splitter. The motion of the mirror causes the path length that the second beam transverses to vary.
The two beams recombine at the same splitter but path length differences (different wavelength)
of the two beams cause both constructive and destructive interferences (interferogram).
The interferogram generated by combining the two beams is oriented towards the sample by the
beam splitter. As it passes through the sample, the sample simultaneously absorbs all the
wavelengths (frequencies) that are normally found in its infrared spectrum. The modified
interferrogrm signal that reaches the detector contains information about the amount of energy that
was absorbed at every wavelength (frequency). The computer compares the modified
interferrogram to a reference laser beam to have a standard comparison. The final interferrogram
contains all the information in one time-domain a signal that cannot be read by a human. A
mathematical process called a Fourier transform must be implemented to extract the individual
frequencies that were absorbed and to reconstruct and plot what we recognize as a typical infrared
spectrum.

A typical infrared spectrum is shown below (Courtesy Pavia)

57
In the case of ultraviolet and visible spectroscopy, the transitions that result in the absorption of
electromagnetic radiation in this region of the spectrum are transitions between electronic energy
levels.

As a molecule absorbs energy, an electron is promoted from an occupied orbital to an unoccupied

orbital of greater potential energy. The most probable transition is from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The energy
difference between electronic levels in most molecules vary from 125 to 650 KJ/mole.

For most molecules, the lowest energy occupied molecular orbitals are the σ orbitals, which
correspond to σ bonds. The 𝜋 orbitals lie at somewhat higher energy levels and orbitals that hold
unshared pair, the nonbonding (n) orbitals, lie at even higher energies. The unoccupied or

58
antibonding orbitals (𝜋 𝑎𝑛𝑑 σ ) are the orbitals of highest energy. The figure below shows a typical
progresssion of electronic energy levels.

qqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqqq
qqqqq@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@
@@@@@

In all compounds, the electrons may undergo several possible transitions of different energies.
Some of the most important transitions are:

THE ORIGIN OF UV BAND STRUCTURE

For atoms that absorbs in the ultraviolet, the absorption spectrum sometimes consists of very sharp
lines as would be expected for quantized process occurring between two discrete levels. For
molecules however, the UV absorption occurs over wide range of wavelengths because molecules
(as opposed to atoms) normally have many excited modes of vibration and rotation at room
temperature. In fact the vibration of molecules cannot be completely ‘frozen out’ even at absolute
zero. Consequently, a collection of molecules generally has its members in many states of vibration
and rotational excitation. The energy levels are quite closely spaced corresponding to energy
differences considerably smaller than those of electronic levels. The rotational and vibrational
levels are thus superimposed on the electrical levels. Thus a molecule may therefore undergo
electronic and vibrational-rotational simultaneously.

59
Question.
A laser cavity is 10.339 96 cm long and is operating at a wavelength of 533.647 8 nm. How many
half-wavelengths are there along the length of the cavity? By how much would the length have to
be changed to increase this number by one? What consequences does this result have for the tuning
of such a cavity? How long does it take for the radiation to complete one round-trip of the cavity
(to four significant figures)?

Answer. Since wavelength 𝜆 and frequency 𝜈 are related by

𝑐 = 𝜈𝜆
𝑛𝜆
𝑑=
2
2𝑑
𝑛=
𝜆

𝑛𝑐
𝜈=
2𝑑

9 LASERS AND LASER SPECTROSCOPY

Therefore the cavity has been increased in length by 0.000 03 cm¼0.3 mm. This means that to
tune the cavity to a half wavelength of the radiation requires an extremely accurate movement of
one of the mirrors forming the cavity.
One round-trip of the cavity covers a distance of 20.680 cm
; time taken ¼ 20:680 cm
2:997 9 _ 1010 cm s_1
¼ 6:898 _ 10
_10 s
The

60