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Lesson Objectives
(4) Fundamentals of
Spectroscopy
Jonyl L. Garcia, M.Sc., RCh.
Assistant Professor
Chemistry Department
SPECTROSCOPIC THEORIES
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At the end of this lesson, the student will be able to:
❑ Define the various spectroscopic terminologies;
❑ Describe the properties of light both as a wave and as a
particle;
❑ Understand the relationship between energy, frequency,
and wavelength of EMR;
❑ Classify EMR according to its region in the spectrum;
❑ Describe the different ways EMR interact with matter;
❑ Differentiate between absorption and emission of
radiation;
❑ State the Beer-Lambert’s Law and its limitations;
❑ Perform calculations involving Beer-Lambert’s Law.
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What is LIGHT?
Maxwell (1873), proposed that visible light Electromagnetic radiation is
consists of electromagnetic waves. the emission and
transmission of energy in the
form of electromagnetic
waves.
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What is LIGHT?

• Planck
– Light is a WAVE
• Einstein
– Light is a PARTICLE – Photons (Lewis)
Now we know how the electrons and photons behave.
• De Broglie But what can I call it? If I say they behave like
– Wave-Particle Dualism particles I give the wrong impression; also if I say that
– Light as both a WAVE and a PARTICLE they behave like waves. They behave in their own
inimitable way, which technically could be called a
quantum mechanical way. They behave in a way that is
like nothing that you have ever seen before.
– Richard Feynman
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Light as a Wave Properties of Waves

• Wave Model
– Describes EMR as an electric field that undergoes
sinusoidal oscillation as it moves through space; it is
characterized by parameters such as wavelength,
frequency, velocity, amplitude, etc.

Wavelength (l) is the distance between identical points on successive

waves.
Amplitude is the vertical distance from the midline of a wave to the peak or
trough.
Wavenumber (𝜈)ҧ is the reciprocal of wavelength (in cm-1)

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Properties of Waves Terms

Frequency (ν) is the # of oscillations of the field per second (Hz). • Irradiance / Radiant Power (P) – Energy per unit time per
unit area (W/m2)
Period (τ) is the time (in s) required for the passage of a successive maxima or
• Amplitude – length of electrical vector at a maximum in a
minima through a fixed point in space. wave
– y = A sin(wt + Φ)
Velocity (v) is the rate at which the wave front moves through a medium (in cm/s
– y - electrical field; A – amplitude; w – angular frequency; t – time; Φ –
or m/s) phase angle

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Electromagnetic Spectra Electromagnetic Spectra

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Exercise #1
A photon has a frequency of
6.0 x 104 Hz. Convert this
frequency into wavelength
(nm). Does this frequency fall
in the visible region?

INTERACTION OF EMR WITH

MATTER

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Common Spectroscopic Methods Based On

EMR
Interaction of EMR with Matter

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Interaction of EMR with Matter as a Wave Interaction of EMR with Matter as a Wave

• Superposition • Diffraction
– When 2 or more waves traverse the same space, a
displacement occur that is the sum of the displacements – A process in which
caused by the individual waves a parallel beam of
– Constructive interference radiation is bent
– Destructive interference as it passes by a
sharp barrier or
through a narrow
opening

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Interaction of EMR with Matter as a Wave Interaction of EMR with Matter as a Wave
Selected refractive indices at λ=589 nm. For references, see the

• Transmission • Refraction extended List of refractive indices.

Material n
– When radiation passes
– Process in which an through an angle through
Gases at 0 °C and 1 atm

incident radiation P0 the interface between 2

Air 1.000293
Helium 1.000036
changes its velocity transparent media having Hydrogen 1.000132
different densities, an
when propagating abrupt change in direction
Carbon dioxide
Liquids at 20 °C
1.00045

through a transparent of the beam is observed Water 1.333

substance, then exits due to the difference in Ethanol 1.36
P velocity of the radiation in
the substance along the 2 media.
Benzene
Solids
1.501

the original direction – When beam passes from a Ice 1.309

of the beam; no less dense to a more dense Fused silica 1.46

frequency change 𝑷 environment, the bending PMMA 1.49

hence no permanent
𝑻= is toward the normal of
the interface
Crown glass (typical) 1.52

𝑷𝟎 Flint glass (typical) 1.62

energy transfer Diamond 2.42

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Interaction of EMR with Matter as a Wave Exercise #2

• Reflection Calculate the percentage loss of intensity due to

– When radiation reflection of a perpendicular beam of yellow light as
crosses an interface it passes through a glass cell that contains water.
between media that Assume that for yellow radiation the refractive index
differ in refractive
index, reflection of glass is 1.50, of water is 1.33, and of air is 1.00.
Ir I0
always occur
– Fraction reflected
becomes greater with
increase in
differences in
refractive index

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Interaction of EMR with Matter as a Wave Interaction of EMR with Matter as a Wave

• Scattering • Rayleigh Scattering

– An incident radiation – Scattering by large
on a matter is molecules or aggregates
transmitted at all of molecules with
dimensions significantly • I – intensity
angles from the
smaller than the • dp – particle diameter
original path, the wavelength of radiation
intensity of scattered • λ - wavelength of
– Wavelength of scattered
radiation increases incident light
radiation = wavelength
with particle size of incident radiation

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Interaction of EMR with Matter as a Wave Interaction of EMR with Matter as a Wave

• Mie scattering • Raman Scattering

– Raman scattering effect
– With large particles, scattering can be different in differs from ordinary
different directions. scattering in that part of
the scattered radiation
– Measurements of this type of scattered radiation are suffers quantized
used to determine the size and shape of large frequency changes.
molecules and colloidal particles. – These changes are the
result of vibrational energy
level transitions that occur
in the molecules as a
consequence of the
polarization process
– λscattered < > λincident

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Interaction of EMR with Matter as a Wave

• Polarization
– A process in which
radiation is made to
propagate only in a
single plane in space
– Done using a polarizer

QUANTUM-MECHANICAL
PROPERTIES OF RADIATION

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Quantum-Mechanical Properties of
Radiation
Photoelectric Effect

• Wave model cannot completely explain the When EMR is emitted or

absorbed, a permanent transfer
hν = eVo + ω
absorption or emission of radiation, where there is a of energy from the emitting (KE) (WF)
object or to the absorbing
permanent energy transfer to the absorbing medium medium occurs.
or from the emitting object 1. Photocurrent proportional to
intensity of incident
• EMR is viewed as a stream of discrete particles or radiation.
2. Magnitude of stopping
wave packets (photons or quanta), with the energy voltage depends on
frequency (energy) of
of a photon being proportional to the frequency of incident radiation.
the radiation. 3. Stopping voltage depends on
photocathode material.
4. Stopping voltage is
independent of intensity of
incident radiation.

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Correlation between the wave and particle

property of EMR: Dualism
Exercise #3

Calculate the energy of (a) a 5.3-A X-ray photon and

(b) a 530-nm photon of visible radiation.
Particle property Wave property

ν , E

λ , E
h = 6.626 x 10-34 Js
c = 3.00 x 108 m/s
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Energy States of Chemical Species

1. Atoms, ions, and molecules can exist only in certain
discrete states, characterized by definite amounts of
energy. When a species changes its state, it absorbs or
emits an amount of energy exactly equal to the energy
difference between the states.
2. When atoms. ions. or molecules absorb or emit radiation in
making the transition from one energy state to another, the
frequency v or the wavelength λ of the radiation is related
to the energy difference between the states by the
equation
ABSORPTION 𝑬𝟏 − 𝑬𝟐 = 𝒉𝝂 = 𝒉
𝒄
𝝀
SPECTROSCOPY

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Energy States of Chemical Species Absorption of EMR

• Electronic states • Absorption
– Arises from the motions of
electrons around a – A process in which a
positively charged nucleus chemical species in a
transparent medium
• Vibrational states selectively remove
– For molecules 𝒄 (attenuates) certain
𝑬𝟏 − 𝑬𝟐 = 𝒉𝝂 = 𝒉
– Associated with the energy 𝝀 frequencies of EMR;
of interatomic vibrations there is a transfer of
• Rotational states energy from the
– Arise from the rotation of radiation to the
molecules around their atoms, ions or
center of mass molecules constituting
the sample

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Absorption of EMR Absorption of EMR

• Absorption
– Absorption leads to the • Absorption
excitation of the chemical – Absorption spectrum –
species from the ground
state to an excited state a plot of some
(higher energy). function of the
attenuation of the
– Absorption is only possible if beam of radiation vs.
the energy of radiation wavelength,
matches exactly the energy
difference between the frequency or
ground state and one of the wavenumber.
higher energy states of the
particle

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Absorption by different chemical species Absorption by different chemical species

• Atoms
– Involves the attenuation of only a few frequencies of
radiation
– Leads to electronic transitions ONLY – one or more
electrons of the atoms is raised to higher energy level
– UV-Vis radiation – transitions for the bonding or
outermost electrons
– X-ray – interacts with atomic electrons that are closest to
the nucleus
– Absorption spectrum – consists only of a number of very
narrow absorption lines
• Molecules
– Leads to changes in three types of energy levels
• EElectronic – arise from energy states of its several bonding electrons
• EVibrational – energy associated with interatomic vibrations present
in the molecule
• ERotational – energy due to various rotational motion within the
molecule
– Etotal = Eele + Evib + Erot
– ΔEelec > ΔEvib > ΔErot
• Electronic transition – induced by UV-Vis and X-ray
• Vibrational transition – induced by IR
• Rotational transition – induced by microwave, radio waves or
longer IR radiation

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Line vs. Band Spectra Line vs. Band Spectra

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Types of Molecular Vibrations Relaxation Process

• Relaxation Process
– Lifetime of excited species is brief due to several
mechanisms whereby an excited atom or molecule can
give up its excess energy and relax to its ground state.

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Types of Relaxation Processes Types of Relaxation Processes

• Non-radiative relaxation • Non-radiative

– (a) vibrational deactivation or relaxation – deactivation relaxation
occurring between the vibrational energy level within an – (b) nonradiative
electronic energy level; takes place during collisions deactivation –
between the excited molecules and the molecules of the occurs between the
solvent, where excess energy is transferred to the lowest vibrational
solvent; gain in vibrational energy of solvent is reflected level of an excited
as tiny increase in temperature electronic state and
• Very efficient; short life time 10-15 s the upper
vibrational level of
another electronic
state

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Types of Relaxation Processes

• Radiative
relaxation or
fluorescent
relaxation
– Excess energy is
released as
photons or in the
form of light
QUANTITATIVE ASPECTS OF
SPECTROCHEMICAL
MEASUREMENTS
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Terms Employed in Absorption

Major Classes of Spectrometric Methods
Spectroscopy
• Transmittance
– A beam of parallel radiation of intensity I0 will be
attenuated to intensity I after it passes through a
layer of absorbing solution with a thickness of b
and concentration C, due to the interaction
between the absorbing particles and the photons

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Terms Employed in Absorption

Visible Spectrum Spectroscopy

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Figure 24F-4a p665
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Terms Employed in Absorption Relationship between Absorbance and

Spectroscopy Concentration: Beer-Lambert’s Law

• Absorbance
– Absorbance of solution increases as the attenuation
of beam becomes greater; while transmittance
decrease as attenuation increases (Note: non-linear
relationship)

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Limitations of the Applicability of Beer’s

Law
• Real Limitation
– Beer-Lambert’s Law applicable only for dilute solutions
– At high concentration (> 0.01M), the average distance
between particles of absorbing species diminish to the
point where each particle affects the charge distribution
of its neighbors
– The interaction can alter the ability of particles to absorb
a given wavelength
– Refractive index changes with concentration of solution

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Figure 24-10 p664
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Limitations of the Applicability of Beer’s Limitations of the Applicability of Beer’s

Law Law
• Chemical Deviation • Instrumental deviation with polychromatic
– Deviation from Beer’s law
appear when analyte deviation
undergoes association, – Beer’s law is applicable only when absorbance s
dissociation, or reaction
with the solvent to give measured with monochromatic radiation
products with absorbing – With polychromatic sources, the molar absorptivity
characteristics different
from those of the analyte
of the analyte for each wavelength could differ
– Deviation appears when leading to deviations
increase in analyte
concentration leads to
dimerization /
polymerization

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Limitations of the Applicability of Beer’s

Law
• Instrumental deviation
in the presence of
Stray radiation
– Stray radiation resulting
from scattering
phenomena of prisms,
lenses, filters and
windows
– Stray radiation could
differ greatly in
wavelength from the
principal radiation and
may not have passed
through the sample or
the solvent.

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EMISSION SPECTROSCOPY

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Emission of EMR Emission and Chemilumiscence

• Atoms, ions, and molecules that are excited to

higher energy level (e.g. through bombardment with
electrons, exposure to high-voltage ac spark, heat
treatment in flame or arc, or exposure to a source
of EMR), can release their excess EMR

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Atomic Emission Spectroscopy Types of Emission Spectra

• Line spectra – atoms

• Band spectra – for molecules
• Continuous spectra – very broad, no peak, no line

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Types of Emission processes

• Fluorescence
– takes place more rapidly than phosphorescence
– Generally complete in 10-5 s or less from the time of
excitation
• Phosphorescence
– May extend for minutes or even hours after irradiation
has ceased

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Photoluminescence

THANK YOU FOR YOUR

ATTENTION!

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