Unit 7-Instrumentation Optical Measurments.

ASM-804 Advanced
Atmospheric Chemistry and Air Quality

IGSSA-AAU
Unit 7- Part I –Instrumentation- Optical
measurments
Solomon Bililign
Professor , Physics and Applied Sciences and Technology
North Carolina A&T State University, Greensboro, NC
Adjunct Professor-IGSSA
Topics
• Experimental set up for optical measurements
• Gas analyzers- theory, principles and operations
 IR detection
 Fluorescence techniques
 Chemiluminescence
• Optical counters-DMA-CPC
• Cavity Ring down spectroscopy
• Photoacoustic Spectroscopy
• Absorption measurements-Aethalometer
• Scattering measurements-Nephelometer
• Low-cost sensors
• Light sources-Lasers
• Light detection: monochromators, photodiode, photomultipliers
Light Sensor UV Lights
NOX O3 CO2
UPLC/DAD-ESI- MFCs Tube Furnace
N2
HR-QTOFMS, Teflon Chamber CO
Filter
GC/EI-MS, IC Zero Air Impinger
Gen. & Filter
and TWSOC Mixing GC
Analyses Fan
Carbon Vent
Trap Rotameters
Platform to identify BrC chromophores Hygrothermometer
NOX
Teflon Lines Barometer
Inlets
or Dryer
CPC
Nephelometer
DMA
or
CRDS
CPC Neb.
APM
PAX, PASS-3
AE33
LANL
ACSM
Light Sensor UV Lights
NOX O3 CO2
MFCs Tube Furnace
N2
Teflon Chamber CO
Filter
Zero Air Impinger
Gen. & Filter
Mixing GC
Fan
Carbon Vent
Trap Rotameters
Hygrothermometer
NOX
Teflon Lines Barometer
Inlets
or Dryer
CPC
Nephelometer
DMA
or
CRDS
CPC Neb.
APM
AE33
ACSM
Tube furnace allows us to produce aerosols under
controlled burning conditions(temperature, air flow,
oxygen content, and amount of fuel burned)
Instrumentations
Smog chambers provide a • RH below detection limit of the
controlled environment to hygrometer range 5-95%
study the formation and the • Chamber Temperature -21C TO 24C
evolution of specific • At the end chamber flushed with zero
compounds and particles air at 15 L/min for 24 hours or until
produced from specific fuel. particle concentration is below 2mg/m2
or NO below 5 ppbv
The smoke and gasses produced from combustion are sent directly to
the chamber via a heated (200 °C), and
• Details ¼-inch OD
of Chamber stainless steel
characterization
transfer tube. AAQR- 3, 467-483, 2019
Instrumentations
Well-mixed volume within 10 to 20 minutes after an injection-
mixing fan inside
0.5 g fuel produces about 600 to 800 µg m−3 of mass loading
in the chamber during smoldering-dominated combustion.
SMPS DMA (TSI-
3081) and WCPC
(TSI-3787) for particle
size distribution
Size selection based Smoldering
Flaming
on electrical mobility Dominated
Dominated
by DMA and pass (MCE<0.9)
(MCE>0.95)
through APM
(Kanomax 3602) to
classify particles by
mass to charge ratio
• Previous lab and field
studies of cookstoves
and open burns favored
the flaming-dominated or
transition regime.
• The tube furnace allows
us to study a wide range
of burning conditions.
• Pokherl et al, 2021
Gas analyzers
Most gas detection uses
spectroscopy
• Interaction of matter with
electromagnetic radiation
– UV, visible light, or IR
– X-rays, gamma rays
• Absorption spectroscopy
– Target molecule absorbs the light
• Emission spectroscopy
– Incident radiation causes molecule to emit
light at a new wavelength
Absorption of radiation by gas molecules
…requires quantum transitions in internal energy of molecule.
• THREE TYPES OF TRANSITION
– Electronic transition: UV radiation (<0.4 mm)
• Jump of electron from valence shell to higher-energy shell,
may result in photolysis (example: O3+hn gO2+O)
– Vibrational transition: near-IR (0.7-20 mm)
• Increase in vibrational frequency of a given bond
requires change in dipole moment of molecule
• Very little absorption takes place at visible wavelengths (VIS: 0.4-0.7 mm)
• Gases that absorb radiation in the 5-50 μm range where the Earth emits are
called greenhouse gases; this requires vibrational-rotational transitions
– Rotational transition: far-IR (20-100 mm)

• Increase in angular momentum around rotation axis
Light-matter interaction-Review
Rigid-Rotor model of diatomic molecule
Non-Rigid Rotation
Non-Rigid Rotation
Diatomic Molecules
Diatomic Molecules
Diatomic Molecules
Diatomic Molecules
Vib-Rot spectra – simple model
Vib-Rot spectra – simple model
Infrared region
LIMIT OF RED LIGHT: 800 nm, 0.8 mm, 12500 cm-1
NEAR INFRARED: 0.8 -2.5 mm, 12500 - 4000 cm-1
MID INFRARED: 2.5 - 50 mm, 4000 - 200 cm-1
FAR INFRARED: 50 - 1000 mm, 200 - 10 cm-1
Divisions arise because of different optical materials and

instrumentation.
Infrared (IR) Spectroscopy
•IR deals with the interaction of infrared radiation with
matter. The IR spectrum of a compound can provide
important information about its chemical nature and
molecular structure.
•Most commonly, the spectrum is obtained by measuring
the absorption of IR radiation, although infrared emission
and reflection are also used.
•Widely applied in the analysis of organic materials, also
useful for polyatomic inorganic molecules and for
organometallic compounds.
Vibrations – relative positions of the atoms change while the average position
and orientation of the molecule remain fixed.
Fundamental Vibrations
Selection Rules
The energy associated with a quantum of light may be transferred to the
molecule if work can be performed on the molecule in the form of displacement
of charge.
Selection rule:
A molecule will absorb infrared radiation if the change in vibrational states
is associated with a change in the dipole moment (m) of the molecule.
µ = qr
q: electrical charge, r: directed distance of that charge from some defined origin
of coordinates from the molecule.
Dipole moment is greater when electronegativity difference between the atoms
in a bond is greater. Some electronegativity values are:
H 2.2; C 2.55; N 3.04; O 3.44; F 3.98; P 2.19; S 2.58; Cl 3.16
• Vibrations which do not change the dipole moment are Infrared Inactive
(homonuclear diatomics).
Infrared Spectroscopy
A) Introduction
1.) Infrared (IR) spectroscopy: based on IR absorption by molecules as undergo

vibrational and rotational transitions.
rotational transitions
Potential Energy (E)
Vibrational transitions
Interatomic Distance (r)
Potential energy resembles classic Harmonic Oscillator

2.) IR radiation is in the range of 12,800 – 10 cm-1 or l = 0.78 – 1000 mm
- rotational transitions have small energy differences
• ≤ 100 cm-1, l > 100 mm
- vibrational transitions occur at higher energies
- rotational and vibrational transitions often occur together
3.) Typical IR spectrum for Organic Molecule

% Transmittance
Wavenumber (cm-1)
iii.) Types of Molecular Vibrations
Bond Stretching Bond Bending
symmetric In-plane rocking
asymmetric In-plane scissoring
Out-of-plane wagging
Out-of-plane twisting
symmetric asymmetric In-plane scissoring
Out-of-plane twisting In-plane rocking Out-of-plane wagging

iv.) Number of Vibrational Modes:
- for non-linear molecules, number of types of vibrations: 3N-6
- for linear molecules, number of types of vibrations: 3N-5
- why so many peaks in IR spectra
- observed vibration can be less then predicted because
• symmetry ( no change in dipole)
• energies of vibration are identical
• absorption intensity too low
• frequency beyond range of instrument
Examples:
1) HCl: 3(2)-5 = 1 mode
2) CO2: 3(3)-5 = 4 modes
- + - moving in-out of plane
See web site for 3D animations of vibrational modes for a variety of molecules
http://www.chem.purdue.edu/gchelp/vibs/co2.html
v.) IR Active Vibrations:
- In order for molecule to absorb IR radiation:
• vibration at same frequency as in light
• but also, must have a change in its net dipole moment
as a result of the vibration
Examples:
1) CO2: 3(3)-5 = 4 modes m = 0; IR inactive
d- 2d+ d-
m > 0; IR active
d- 2d+ d-
- + - m > 0; IR active
d- 2d+ d-
degenerate –identical energy single IR peak
2d+
m > 0; IR active
d- d-
Infrared Spectrum
of Carbon Dioxide
Coupled Interactions
• When two bond oscillators share a common atom, they seldom behave
as individual oscillators (unless the individual oscillation frequencies are
widely different).
The frequency of the asymmetric stretching vibration in CO2 is at a

shorter wavelength (higher frequency) than for a carbonyl group in
aliphatic ketones (around 1715 cm–1 ).
–> there must be strong mechanical coupling or interaction!
Example: C–O stretching band in
Methanol: 1034 cm –1
Ethanol: 1053 cm –1
not an isolated stretching vibration, but rather a coupled symmetric
stretching invloving C–C–O stretching
Main uses of IR spectroscopy:
1. Fundamental chemistry
Determination of molecular structure/geometry.
e.g. Determination of bond lengths, bond angles of
gaseous molecules
2. Qualitative analysis – simple, fast, nondestructive

Monitoring trace gases: NDIR.Rapid, simultaneous
analysis of GC, moisture, N in soil. Analysis of fragments
left at the scene of a crime
Quantitative determination of hydrocarbons on filters, in
air, or in water
Dispersive IR spectrophotometers
Modern dispersive IR spectrophotometers are invariably double-beam
instruments, but many allow single-beam operation via a front-panel switch.
Simplified diagram of a double beam infrared spectrometer

Near-infrared and Far-infrared absorption
The techniques and applications of near-infrared (NIR) and

far-infrared (FIR) spectrometry are quite different from those
discussed above for conventional, mid-IR spectrometry.
Near-infrared: 0.8 -2.5 mm, 12500 - 4000 cm-1

Mid-infrared: 2.5 - 50 mm, 4000 - 200 cm-1
Far-infrared: 50 - 1000 mm, 200 - 10 cm-1
Gas Analyzers
Gas analyzers work on the
principle of absorption of light
by the gas under test.
Absorption analyzers need only
shine a beam of light through
an unheated sample chamber,
then measure how much of
specific wavelengths were
absorbed by the sample. The
amount of light absorbed is
proportional to the
concentration of the
component in the fluid which
absorbed light
Working principle:
In every absorption-type optical analyzer, the fundamental equation
relating photon absorption to substance concentration is the Beer-
Lambert Law:
Where; A = Absorbance a = Extinction coefficient for photon-absorbing

substance(s) b = Path length of light travelling through the sample c =
Concentration of the photon-absorbing substance in the sample I0 =
Intensity of source (incident) light I = Intensity of received light after
passing through the sample
Dispersive spectroscopy:
The dispersive spectrometer is constructed
as shown in the picture. The process fluid
is made to pass through a chamber.
Whitebeam of light is passed through the
transparent walls of the chamber. The light
escaped from the chamber is diffracted
using a diffraction grating to disperse the
different wavelengths of light from each
other so they may be independently
measured.
Where some wavelengths of that light
would be attenuated by interaction with the
process fluid molecules. In this illustration,
the sample gas absorbs some of the yellow
light wavelengths, resulting in less yellow
light reaching the detector array.
Principles of Gas analyzers-Non-
dispersive spectroscopy:
Industrial non-dispersive analyzers typically use either infrared
or ultraviolet light sources, because most substances of interest
absorb wavelengths in those regions rather than in the visible
light spectrum.
There are NDIR, NDUV, NDVIS non-dispersive analyzers.
NDIR - uses infrared light NDUV - uses ultraviolet light beam
NDVIS - uses visible light
There are two types of non-dispersive analyzer
 Single-beam analyzer
 Dual-beam analyzer
Single-beam analyzer:
Non-dispersive analyzers employ
the principle of spectrographic
absorption to measure how much
of a particular substance exists
within a sample. NDIR gas
analyzers shine light through a
windowed sample chamber
(typically called a cell ), through
which a fresh flow of process gas
continually moves. Certain
“species” (compounds) of gas
within the sample stream absorb
part of the incident light, and
therefore the light exiting the cell
becomes partially depleted of
those wavelengths
Dual-beam analyzer:
One way to improve on the single-
beam analyzer design is to split the
light beam into two equal halves, then
pass each half-beam through its own
cell.
Only one of these cells will hold the
process gas to be analyzed – the other
cell is sealed, containing a “reference”
gas such as nitrogen that absorbs no
infrared light. At the end of each cell
we will place a matched pair of
thermopile detectors, connecting these
detectors in series-opposing fashion
so equal voltages will cancel
CO2 analyzer
. The CO2 Analyzer use multi-component analysis by using
Non-Dispersive Infrared (NDIR) sensor technology for
consistent, precise process gas measurement
CO2 analyzer
In a simple NDIR instrument,
Infrared energy passes
through two identical tubes
and falls on a detector. The
first tube is the reference cell
and is filled with a non-
absorbing gas such as
nitrogen. The second tube is
the measurement cell and
contains the gas sample to be
analyzed.
CO2 analyzer
The IR Source continuously sends an IR waves through the gas tubes and detector measures the
intensity of two different wavelengths,
• one at the sample gas absorption wavelength and the other is at reference gas absorption
wavelength. As the reference gas generally contains nitrogen so the detector receives 100%
signal. If the CO2 gas is present in sample gas means the received signal will be attenuated at
the detector side.
• The detector measures these two signals, and their difference is proportional to the amount of
absorbing gas in the sample cell .i.e. CO2 gas.
• So Finally, the CO2 gas concentration is measured with the difference in absorption of IR
radiation in the sample and reference cells. CO2 gas concentration measuring unit is ppm.
Why Fluorescence?
Advantages of Fluorescence
• Easy, Fast (eg. vs silver staining)
• Visualize tagged primer strand
Detection of 25 pg of dsDNA
• Multiplexing with PicoGreen Reagent
• High Sensitivity
• Dynamic Range
Principles and Definitions
What is Fluorescence?
Fluorescence is a molecular phenomenon in which a substance
absorbs light of some color (excitation) and almost
instantaneously radiates light of another color, one of lower
energy and thus longer wavelength (emission).
Primary fluorescence- intrinsic property of a substance

Secondary or indirect fluorescence uses dyes
Fluorochromes = dyes
Fluorescent probes or fluorophores are dyes conjugated to
substances
How does it work?
1. laser strikes fluorophore

2. fluorophore absorbs laser energy
3. fluorophore emits light at a
Longer wavelength
Light is collected CCDs or PMTs

Three-Stage Process
of Fluorescence
Excited State
of Fluorophore Relaxed
Excited
S1 ’ 2 State
S1
Photon Absorption
Photon Emission
Energy
1 3
S0 Ground State
of Fluorophore
- Jablonski
The 3 stage Fluorescence Process- Jablonski diagram
1- Excitation: Photon of energy (hvEX)
strikes a fluorophore  excited state
2- Excited State Lifetime: Energy

dissapated by:
a. Relaxed state  emission
b. Quenching, energy transfer
Quantum yield =
# fluor photons emitted
# photons absorbed
Most efficient are 0.3 – values reduced by
quenching- eg photobleaching
3- Fluorescence Emission: Photon of

energy (hvEM ) is emitted
Due to energy dissapation in 2, emitted
photon is of lower energy and longer
wavelength- Stoke’s Shift
Excitation and Emission Spectra
Effect of Excitation Wavelength on
Fluorescence Emission
Excitation Wavelength Choice
• Fluorescence intensity is directly affected
• Emission wavelength is not directly affected
• Excitation can occur over a distribution of
wavelengths, not just at one wavelength
• Selecting dyes with larger Stokes shifts allows
for excitation closer to the absorbance
maximum
• Choice exists with the III and III plus (no choice
for ABI, II or II e)
Emission Wavelength Choice
• The percentage of the signal that is
captured depends in great part on
emission filter wavelength choice.
• Emission filters are selected to

• maximize fluorescent signal emission
• attenuate (block) the excitation light- laser
light
Factors in emission filter selection:
• Spectral performance of Optical filters
• Laser excitation wavelength (need to block it)
• Dye emission spectra (need to collect it)
• Fluorescence emission occurs over a
distribution of wavelengths (blocking)
• Spectral bandwidth of dyes (need to isolate them)
• Spectral overlap when multiplexing

Some monitors use
fluorescence- eg. SO2
• SO2 + hn214nm  SO2*

• SO2*  SO2 + hn330nm
• Signal at 330 nm is a function of:
– Intensity of 214 nm light
– Absorption coefficient of SO2
– Decay rate of SO2* to SO2
Pulsed Fluorescence SO2, H2S, CS
Analyzer Working Principle
The Pulsed Fluorescence Analyzer operates on the principle that H2S can be converted to
SO2.
• SO2 molecules absorb ultraviolet (UV) light and become excited at one wavelength, then
decay to a lower energy state emitting UV light at a different wavelength. Specifically,
The sample is drawn into the analyzer through the SAMPLE bulkhead, as shown in Figure.
From the bulkhead the sample is either shunted to a converter or bypasses the converter
and is led straight through to a hydrocarbon kicker.
When sample goes through the converter, the instrument response represents the
combined Sulphur (CS) reading, that is, the sum of SO2, H2S, and any residual reduced
Sulphur species. When bypassing the converter, the instrument reads SO2 only. The
difference between the two signals is the inferred H2S reading.
• The sample, whether coming directly from the bulkhead or processed in the converter, then flows through a
hydrocarbon kicker. The kicker removes hydrocarbons from the sample by forcing the hydrocarbon molecules to
differentially permeate through the tube wall. The SO2 molecules pass through the hydrocarbon kicker
unaffected.
• The sample then flows into the fluorescence chamber, where pulsating UV light excites the SO2 molecules. The
condensing lens focuses the pulsating UV light into the mirror assembly. The mirror assembly contains four
selective mirrors that reflect only the wavelengths which excite SO2 molecules.
• As the excited SO2 molecules decay to lower energy states they emit UV light that is proportional to the SO2
concentration. The bandpass filter allows only the wavelengths emitted by the excited SO2 molecules to reach
the photomultiplier tube (PMT). The PMT detects the UV light emission from the decaying SO2 molecules. The
photodetector, located at the back of the fluorescence chamber, continuously monitors the pulsating UV
light source and is connected to a circuit that compensates for fluctuations in the UV light.
• As the sample leaves the optical chamber, it passes through a flow sensor, a capillary, and the shell side of the
hydrocarbon kicker. The analyzer outputs the SO2, H2S, CS ranges concentration levels to the display.
What is luminescence?
• Luminescence is a general term for the emission of light from a cool object. (In
contrast to, e.g., incandescence – the emission of light from a hot piece of metals such
as the filament in a light bulb.) There are many examples of naturally occurring
luminescence. Most of these fall into one of 3 categories:
• Phosphorescence: Absorption and slow re-emission of light. Most commonly
observed in minerals.
• Fluorescence: Absorption and fast re-emission of light. Seen in deep sea organisms
and some insects and plants.
• Chemiluminescence: Emission of light driven by a chemical reaction. The most
common form of natural luminescence (often called “bioluminescence”). Seen in
aquatic organisms, insects and plants.
Chemiluminescence
• Chemiluminescence is the generation of light by a chemical

reaction. This is the most common form of luminescence in
living organisms. Insects like fireflies use chemiluminescence
to attract their mates, deep sea fish like the Anglerfish use it to
lure prey close to their mouth and microorganisms use it to
signal distress. Recent studies suggest that humans may give
off light too, although this is controversial. To learn more
about the chemistry of chemiluminescence, please see the
poster talking about glow sticks!
Natural examples
An Anglerfish trying to make a

Marine
microorganisms use snack of Marlin and Dory in
chemiluminescence to Finding Nemo. The real fish is to find their mates.
signal distress – in this almost as scary. Fireflies use
case, being disturbed
by the waves. chemiluminescence
NO2 chemiluminescence
Excitation is caused by a
chemical reaction
Older technology
NO+O3  NO2* + O2
Dominant pathway:
NO2*+M  NO2
Minor pathway:
NO2*  NO2 + hn1200nm
https://instrumentationtools.com/chemiluminescence/
Detect NO and NO2 by converting NO2 to
NO
Chemiluminescent NO2 challenges
• NO2 is not detected directly
• Many species can interfere and appear as “NO2”
• Mo catalyst can become saturated or degrade over
time
• Problematic when NO2 is low
Aerodynamic Diameter
Aerodynamic Diameter The aerodynamic diameter of a particle is defined as that of a
sphere, whose density is 1 g cm −3 (cf. density of water), which settles in still air at the same
velocity as the particle in question
The definition of the aerodynamic

diameter da is given by
𝒔
𝒂
𝒐
where μ is the viscosity coefficient
of air, us is the particle settling
velocity, ρ0 = 1 g/cm3 is the unit Water
1 gm / cm3
density or density of water, and g is
the gravitational acceleration.
Hinds
Inertia based
instruments Cascade
Impactor
https://www.sciencedirect.com/topics/engineering/cascade-impactor
Inertia based
instruments-
Cyclone
W. Lindsley, B. Green, F. Blachere, S. Martin, B. Law,

P. Jensen, et al. NIOSH Manual of Analytical
Methods; 5th Edition; Chapter BA March 2017 2017
Optical Particle Counter (OPC): ~ 100 nm to 5 mm
From-James Smith and Steven Massie NCAR presentation
size limits defined by Mie scattering, which are used to interpret integrated scattered
intensity.
Advantages: Disadvantages:
• Can detect very small particles • too sensitive to small changes
in
• Non-intrusive • refractive index
• Instantaneous and continuous • scattering angle
information • particle size
• particle shape
Condensation Particle Counter (CPC):
~1.5 nm to 0.5 mm
http://www.cas.manchester.ac.uk/restools/instruments/aerosol/cpc/
Condensation Particle Counters

(CPCs) detects particles by
exposing them to a region that is
supersaturated with vapor (usually
butanol), thus allowing particles to
grow to a size that can be optically
detected.
• Saturate an aerosol with water or alcohol vapor

• Cool by adiabatic expansion or flow through a cold tube
• Nuclei will grow to ~ 10 mm
• Every nuclei grows to a droplet
• Measure the number of droplets with an e.g. single particle optical
counter
Electrical Mobility
• When a charged particle is placed in an electric field it is acted by a force FE= qE=neE where q is
total charge which is n number of charged particles times electron charge
• For a particle motion in the stokes region, (The particle should be smooth, solid, and spherical in
shape. The density should be uniform. The flow should be laminar) the terminal velocity is obtained
by equating FE = FD
Cc = Cunningham slip correction factor,
VTE-Terminal electrostatic velocity

In terms of Mechanical Mobility B that defines the ratio between the velocity of the particle and the external
force associated with its motion
Electrical Mobility
For Re >1 is common for electrostatic motion is greater than for
settling since electrostatic force is much greater than gravity,
Solving for CD
𝑑𝜌𝑉
Multiply both sides by Re2, where Re = 𝜂
It is convenient to express the ability of the particle to move in an electric field in terms of the particle’s mobility Z,
charge, and Electric field strength.
𝑽𝑻𝑬 𝒏𝒆𝑪𝒄
, Re<1
𝑬 𝟑𝝅𝜼𝒅
Electrical Mobility
When a charged particle suspended in a gaseous medium is placed in an electric field, the particle
experiences a force which is dependent on its charge and the strength of the electric field. This force
causes the particle to accelerate along the field lines. This acceleration is opposed by viscous forces within
the fluid, which are dependent on particle size and fluid viscosity, and which increase with increasing
particle velocity. Thus, a particle reaches its terminal velocity when electrical and viscous forces are
balanced.
Electrical mobility is described by the following equation, which is derived from Stokes’ law.
Zp= n e Cc / 3 π η Dp
where Zp = Electrical mobility, n = Number of charges on the particle, e = Elementary charge, Cc =
Cunningham slip correction, η = Dynamic viscosity of air and Dp = Radius of particle.
The Cunningham slip correction accounts for the discrete nature of the dynamic viscosity due to the
particle being bombarded by individual air molecules. This factor becomes increasingly important for
smaller particles but is relevant over the whole size range measured by DMA systems.
DMA - Differential Mobility Analyzer
A charged particle will be pushed in the direction of VTE by the

electric field E between the two plates.
Highpoint University 11/5/21 Hinds 86

Differential Mobility Analyzer (shown
below, a “Nano DMA”)
inlet
sheath air
HV
outlet
Efficiently size-selects charged

particles for collection and
TSI, Inc. analysis.
Chen et al., 1998
More on DMA
• In the atmosphere most aerosol is charged, often with multiple elementary charges, for
classification by electrical mobility to be meaningful in terms of particle size, the aerosol
must be given a known charge distribution.
• In addition to the multiple charging issues, the output of a DMA is also not completely
monodispersed for several other reasons, including particle diffusion and turbulence.
• For spherical particles mobility diameter is equivalent to volumetric diameter, however
for non-spherical particles this is not the case. For such particles mobility diameter is a
function of particle shape and orientation, as it is the cross-sectional area perpendicular
to the direction of particle motion which determines the drag on the particle and hence
electrical mobility.
• Additionally, the electric field within the DMA may cause certain types of non-spherical
particle to align with the field.
89
Experimental
Details-
Extinction
What is CRD spectroscopy ?
• CRDS is a sensitive absorption technique in which the rate of absorption in
an optical cavity is measured
• It has significantly high sensitivity
1. The effective absorption path length is very long
2. The sensitivity is independent of intensity fluctuations of the light source
• A laser pulse coupled into an optical cavity
• The decay time is determined by measuring the time dependence of the light leaking out of
the cavity
• From the decay time the rate of absorption is determined directly providing the losses on an
absolute scale
Cavity Ring Down Spectroscopy
• CRD spectroscopy is a sensitive absorption technique in which the rate of
absorption rather than the magnitude of the absorption of a light pulse confined
in an optical cavity is measured.
• The sample is placed inside a high-finesse optical cavity consisting of two
highly reflective mirrors and a short laser pulse is coupled into the cavity.
• Instead of measuring the total intensity of the light exiting the cavity, one
determines the decay time by measuring the time dependence of the light
leaking out of the cavity.
Direct Overtone Photolysis
• In polyatomic molecules containing O-H, C-H and N-H groups, the small mass
of hydrogen gives rise to X-H stretching at considerably higher frequency than
other vibrational modes.
• These modes can have direct excitation from the ground vibrational level to
several excited levels (“overtone transitions”).
• If the vibrational level accessed in this way lies above the dissociation limit,
dissociation is followed.
Direct Overtone Photolysis(contd.)
• The rate of photolysis or photodissociation of a reaction is given as
A + hν B+C
d[A]/dt = jA[A]
Where jA is the the rate coefficient for photolysis and it is a function of
jA = ∫ σA(λ,T) Φ(λ, T) I(λ)d λ
• σA(λ,T) is the absorption cross section for A.
• Φ(λ, T) – is the quantum yield for dissociation
• I(λ)- is the intensity of light
Beer’s Law (a.k.a. Lambert-Beer Law)
dz
I0 I
Light Detector
Source
L
dI    I  dz
IdI L
    dz
I0 I 0
I(z)  I0 exp[L]
  Absorption (Extinction) Coefficient

 (cm-1) = NAbs (cm-3)  (cm2)
If  is known, N can be determined absolutely
Direct Absorption in Atmospheric Chemistry
1. Differential Optical Absorption Spectroscopy
Active Passive
Spectrometer
Spectrograph Lamp
~10 km
True I0
• Generally applicable to
UV and visible absorbers
Differential
• Key to sensitivity for
Absorption
atmospheric trace species
is path length !
Cavity Enhanced Spectroscopy
Optical Cavity
Laser Detector
• Light introduced and detected through a mirror rather than through a

hole in a mirror
• Light intensity inside of the optical cavity depends on a number of

factors, and can be much smaller or much larger than the incident
intensity
• Path length is no longer a well-defined quantity !
• But …. effective or average path length may be very (very, very) long
Limited partly, but not exclusively, by mirror reflectivity
• So …. offers potential for very high sensitivity absorption (or extinction)

spectroscopy
Cavity Ring-Down: Absorption (Extinction) Spectroscopy
Absorber [A]
I
z LA
d Mirror reflectivity = R
•The detector receives a series of pulses that are separated by a round-trip time T, which is defined as
2𝑑
𝑇=
𝑐
The detector receives a series of pulses separated by the roundtrip time t = 2d/c with decreasing power from
pulse to pulse.
P1  T 2 e L P0
After one pass through cavity:  is the absorption coefficient.
After each round trip the pulse power decreases by an additional factor
R 2 Exp(2LA )
T = 1− R− A << 1- Transmission is very small
THEORY
Where α is the absorption coefficient, P1 is the updated power, Po is the initial power, and T is the
transmission. After each round trip, the pulse power decreases by an additional factor of the mirror
reflectivity, R, R2 Exp (-2αLA). It is important to note that transmission is very small, so T=1-R-A <<
1 where A represents all cavity losses (due to scattering, absorption etc.).
After m roundtrips the power would have decreased to
𝑃 = 𝑅𝑒 𝑃
After m-rounds the power has decreased to:
Pm  (Re LA ) 2 m P1  [(1  T  A)e LA ]2 m P1

Pm  P1e 2 m[ln R LA ]  P1e  2 m[T  ALA ]
THEORY
For highly reflective mirrors used in CRDS, R = -(T+A) in the above approximation or T= 1-R if other loses are
ignored. The loss in intensity (Power) of the pulse with distance is governed by is given by
𝑑𝑃 1−𝑅
=− 𝑃
𝑑𝑧 𝑑
Distance travelled by the beam z = ct, where c is the speed of light and t the time using dz = cdt in the equation
above we have
𝑑𝑝 𝑐
= 1 − 𝑅 𝑑𝑡
𝑝 𝑑
THEORY
Which leads to an exponential decay function defined as
𝑡
𝑃 𝑡 = 𝑃 exp(− )
𝜏
Where,
𝑑
𝜏 =
𝑐(1 − 𝑅)
On the other hand, when there is gas or particle in the cavity according to Beers law the loss in power is
proportional to the extinction coefficient as
𝑑𝑝
= −𝛼𝑑𝑧
𝑝
THEORY
If the detector time constant is large compared to the pulse width it will just detect the envelope of the pulse and
record an exponential decay with decay time, defined as
𝑑
𝜏 = 𝑐
𝑇 + 𝐴 + 𝛼𝐿
The differential cavity loss is therefore
𝑑𝑝 𝑐(1 − 𝑅) 𝑐𝛼
= + 𝑑𝑡
𝑝 𝑑 𝑅
THEORY
𝑤𝑖𝑡ℎ 𝑅 = we can solve the Equation above to get
𝑐𝛼 1 𝑡
𝑃 𝑡 = 𝑃 exp(− + 𝑡 = 𝑃 exp(− )
𝑅 𝜏 𝜏
Minimum detectable absorption is limited by the

Therefore, the cavity time constant is reflectivity R, the unavoidable losses A of the
= + resonator and accuracy of measuring to and t1
1  R  t 
The extinction coefficient αext (m-1) is given
 
RL  1 1  L  to  min
  [ A]    
c t t0  Minimum detectable absorption =
Cavity Ring-Down
Absorption (Extinction) Spectroscopy
Define: d
RL 
LA
RL 1 1 
  [ A]    
c t t0 
Minimum detectable absorption is limited by the reflectivity R, the unavoidable losses
A of the resonator and accuracy of measuring to and t1
1  R  t 
Minimum detectable absorption =  
L  to  min
Ring-down time- related to cross sections
I0
Extinction Particle number
coefficient density
(m-1) (particles•m-3)
Intensity
Extinction cross
1 1 1 section
      Nabs  (m •particle-1)
2
c t t 0 
I0/e
Without sample
With sample
Time
 ext (l )   ab ,aero (l )   scat , aero (l )   ab, gas (l )   scat , gas (l )

αext,aero(λ) αext,gas(λ)
104
∆t ≈ 6 ns Round trip Length ≈ 2 m
c = 0.3 m ns-1
Round trip time = 6 ns
Laser
• Mode broadening occurs ass ∆t becomes smaller than tR

• Can also think in terms of coherence length vs. cavity length
FSR = c/2d = 0.15 GHz
• Mode overlap ∆npulsed ≥ 3 GHz
∆n/FSR ≥ 20
Net Result: Passive coupling between laser and cavity

Applications to Atmospheric Science
• Measurements of small absorption cross sections
• Laboratory chemical kinetics
• Laboratory measurements of radicals - e.g., photochemistry
• Field measurements I - Atmospheric trace gas detection
• Field measurements II - Aerosol extinction

Stability of the Cavity-Review of Optics
ABCD ray matrices Represent propagation through optical elements
Ray path A thin lens with focal length f
Propagation through a distance d in a z1 z2

medium with index of refraction of 1
Reflection from a Spherical mirror of Radius R
A B 1 0
 2
A B 1 L
 C D  1
C D 0 1 R
L  z 2  z1 Highpoint University 11/5/21 107
CAVITY STABILITY
N
A B For N round trips of the Beam
C D Highpoint University 11/5/21 108

Stable Optical Resonators
g2
R1 = R 2
R = mirror radius of curvature
d = mirror separation
“g parameter” Unstable
g1,2 = 1 - d
R1,2 Plane Mirrors
R=
Stability condition
0 Š g1g2 Š 1 g1
Confocal
(d = R) R
Spherical
(d = 2R)
2R
Unstable
Highpoint University 11/5/21 109

ABCD Matrix for the CRD

Gaussian Beams-Theory
A. Gaussian beam
The electromagnetic wave propagation is under the way of Helmholtz equation
 2U  k 2U  0
Normally, a plan wave (in z direction) will be
U  U 0 exp{ i ( t  k  r)}  U 0 exp(  ikz ) exp(  i t )
When amplitude is not constant, the wave is
U  A ( x , y , z ) exp(  ikz ) exp(  i t )
An axis symmetric wave in the amplitude
U  A (  , z ) exp(  ikz ) exp(  i t ) z
2n
frequency   2n Wave vector k
l

Paraxial Helmholtz equation
Substitute the U into the Helmholtz equation we have:

2
 2
A  2
 2 2
 A  i 2k
2
T 0 where
T
x y
z
One simple solution is spherical wave：
 A1  2  2  x2  y2
A(r )  exp( jk )
z 2z

The equation A
 A  i 2k
2
T 0
z
has the other solution, which is Gaussian wave：
 W0 2 2
U (r )  A0 exp[ 2 ]exp[ikz  ik  i ( z )]
W ( z) W ( z) 2 R( z )
where
z
W ( z )  W0 [1  ( ) 2 ]1/ 2 z0 is Rayleigh range
z0
z0 2
R ( z )  z[1  ( ) ] q parameter
z
z 1 1 l
 ( z )  tan 1  i
z0 q( z ) R( z )  W 2 ( z )
l z0 1/ 2
W0  ( )  W ( z) z 0  W (0)

Gaussian Beam
E
Beam
radius
z=0

Electric field of Gaussian wave propagates in z direction
A0 ( x 2  y 2 ) x2  y 2
E ( x, y , z )  exp[ 2
]  exp[ik (  z )  i ( z )]
W ( z) W ( z) 2 R( z )
Physical meaning of parameters
z 2 1/ 2
 Beam width at z W ( z )  W0 [1  ( ) ]
z0
 W02
z0 
 Waist width W0  W (0) l
 W02 2 z
 Radii of wave front at z R ( z )  z[1  ( ) ]  z[1  ( 0 ) 2 ]
lz z
lz 1 z
 Phase factor  ( z )  arctan  tg
 W02
z0
Gaussian beam at z=0
A0 r2 r 2  x2  y2 E
E ( x, y,0)  exp[ 2 ] where, A0
W0 W0 W0
Beam width:
z 2 1/ 2
W ( z )  W0 [1  ( ) ] will be minimum A0
z0 eW0
wave front
    W 02   
2
lim R ( z )  lim  z 1       -W0 W0

z 0 z 0
   l z   
at z=0, the wave front of Gaussian beam is a plan surface, but the
electric field is Gaussian form
W0 is the waist half width

Laser cavity modes
Aethalometer Model • The determination of the Black Carbon concentration is
based on the measurement of light absorption on a filter loaded
AE33 with aerosols:
A. Cuesta-Mosquera, G. Močnik, L. Drinovec, T. Müller, S. Pfeifer, M. Minguillón,
et al., AMT, 14, 3195–3216, 2021
• Photoacoustic spectroscopy (PAS)
• is the measurement of the effect of absorbed electromagnetic energy
Acta Phys. Sin., 2019, 68(7): (particularly of light) on matter by means of acoustic detection. The absorbed
074202. energy from the light causes local heating and through thermal expansion a
pressure wave or sound. A photoacoustic spectrum of a sample can be recorded
doi: 10.7498/aps.68.20182084 by measuring the sound at different wavelengths of the light.
Pressure vs. A: P = 0; P = P0
Position Graph B: P > 0; P = Pmax
animation
P C: P < 0; P = Pmin
B
x
A
C
l
Photo-Acoustic effect principle
Modulated Light
Absorption: Ia = αI0
Absorption
Ia
T 
C p V
Local Heating
V  V0 (  T )
Thermal Expansion
Pressure  (v ac2 )( T )

Pressure Wave =
Sound wave
• An absorption cell with volume V may contain N absorbing molecules, which can be
excited into the energy level Ei = Ek +hν by absorption of a photon hn
• If the excited molecule collides with other atoms or molecules in the cell, it can transfer
its excitation energy into translational energy. If N1 molecules are excited, the kinetic
energy Ekin = 3/2 NkT of the species, and therefore the temperature T of the gas, increases
by
• For a closed cell, the total number of molecules

N is constant. A temperature rise therefore
increases the gas pressure p = nkT with
n = N/V by Δp = nkΔT.
• The energy of the absorbed photons is converted into kinetic energy resulting in a
123
pressure increase.
Photoacoustic Spectroscopy
Theory
Introduction
The photoacoustic (PA) or optoacoustic (OA) effect,
i.e. the generation of acoustic waves due to the
absorption of modulated electromagnetic waves, is an
old effect, discovered by Bell in 1880.
This effect is weak; only a very small fraction (<1ppm)
of the absorbed optical energy is converted into
acoustic energy.
PA spectroscopy in gases
 Kreuzer (1971) reported that an ultra low gas
concentration can be detected by OA using an infrared
laser beam as a light source.
A sensitivity limit of a concentration of 10-8 of methane
in nitrogen was demonstrated, and a limit as low as
10-13 could be expected with an improved light source.
Theory
 First step: Optical absorption, which results in the production of
excited states.
 Let’s take a two-level system, which involves the ground state and
the excited state (N and N`)
 N` can be calculated using the rate equation as:
…1
Where Ar is the radiative decay rate of the excited state, An is the non-radiative
decay rate due to collisions of the excited state, and R is the excitation rate due
to the light beam of flux Φ photons per cm-2 sec-1 with an absorption cross
section σ cm2.
Theory cont..
 In many cases, the modulation frequency of the light is slow (~kHz
or less) compared to the excited-state decay rate.
 Furthermore, the light intensity is usually weak enough so that
(N>>N`) and the stimulated emission from the excited state can be
neglected. (slow modulation and weak light)
…2
Where the lifetime of the excited state
Theory cont..
 Heat production rate (H) due to the excited-state density N`
(which depends on position r and time t, because Φ is a function
of r and t) is given by:
…3
Where E` is the average thermal energy released due to

a non-radiative de-excitation collision of the excited
state.
Theory cont..
 If the deexcitation collision results in converting the excited state
to the ground state, then the deexcitation energy is simply the
energy of the excited state with respect to the ground state.
 Equation 3 states that heat source term for the OA signal is
proportional to the product of molecular density (N), photon
absorption rate Φσ, probability for nonradiative relaxation of the
optically excited state An, and the heat energy released per
deexcitation E`.
Theory cont..
 Instead of that, we may rewrite equation 1 as:

…4
where we have again assumed the absence of optical

saturation, i.e., we have assumed N`<<N or R<<τ-1.
The incident light flux is assumed to be sinusoidally
modulated, i.e.,
…5
Theory cont..
 Where only the real part has physical meaning
 We may drop the constant in equation 5 since we are interested
only in the modulated heat source which generates a
corresponding OA signal.
 The solution of equations 4 and 5 is:
…6
where
Theory cont..
• Ψ is the phase lag of the modulation of the excited-state
density compared to the optical excitation, and is large when
the excited state decays more slowly than the modulated rate
of the light intensity.
• Note that equation 6 reduces to equation 2 in the limit when
• The heat generation term H corresponding to equation 6 is

again given by equation 3.
Theory cont..
• As seen in the schematics, the next step in the theory is the
generation of acoustic waves by the heat source H(r,t) of equation
3.
• Inhomogeneous wave equation relating the acoustic pressure p
and the heat source H:
…7
After Morse and Ingard
(1968)
Where c is the velocity of sound and is the ratio of specific heats of the
gas; all dissipative terms have been neglected.
Theory cont..
• Equation 7 is usually solved for the sinusoidal modulation case by
expressing the Fourier transform of p in terms of “normal acoustic
modes” pj which satisfy the appropriate boundary conditions. Thus
…8
with the normal mode pj being solutions of the homogeneous wave
equation, i.e.,
Theory cont..
• pj must be chosen to satisfy the boundary condition that the gradient of p
normal to the cell wall vanish at the wall, since acoustic velocity is
proportional to the gradient of p and must vanish at the wall.
• The resultant orthonormal modes in the cylindrical geometry are given by:
after Morse and Ingard (1968)
with a corresponding angular frequency ωj given by …9
… 10
Theory cont..
• Here gj is a normalization constant; L is the length and R0 the
radius of the gas cell; (r,φ,z) are the cylindrical coordinates of a
spatial point; k, m, and n are the longitudinal, azimuthal, and
radial mode numbers; Jm is a Bessel function; and αmn is the nth
solution of the equation dJm/dr = 0 at r = R0.
• The condition of vanishing pressure gradient at the cell wall
requires that the acoustic pressure p(r,ω) be expressed as linear
combinations of eigenmodes pj of the form of equation 9 for a
cylindrical geometry.
Theory cont..
• Solving the expansion coefficients Aj(ω)
• Fourier transform of equation 7 is:
… 11
• Substituting equation 8 in the above equation and using the

orthonormal conditions for the eigenfunctions pj, we may solve
for Aj as:
… 12
Theory cont..
• Here V0 is the cell volume, Qj is the quality factor for the acoustic mode Pj (
pj* ) is the complex conjugate of pj), and the integral is over the volume of
the cell.
• Qj accounts for the mode damping and avoid the physically unreasonable
situation of  ’ as
• Equation 12 may be further simplified for the case H being given by
equations 2 and 3. In this case
Here we have lumped the space- and time-independent coefficients of

Φ0(r) together as the coefficient q.
Theory cont..
• We also assumed that the light beam is Gaussian, i.e.,
where a is the beam radius; beam propagates along the axis of cell
so that only eigenmodes are of the form of equation
With an eigenfrequency ωj given by
Special case: Beam along the axis of cylinder OA cell in weak absorption limit, and only
Normal modes can be excited by the heat source, i.e., we need only the radial normal modes.
Theory cont..
• The amplitude of the lowest-order radial pressure mode (j=1) is
then given by equation 12 as:
Where,
g1 = normalization factor for , and L = cell length
and we have used

Theory cont..
• Close to resonance (ω=ω1+δ; δ being small ), this equation reduces to:
… 13
 This equation contains the basic physics of the operation of

a resonant OA cell.
 Resonant enhancement of the amplitude of the radial
pressure j=1 is obtained when the fractional detuning from
resonance δ is less than (2Q1)-1.
 In general, larger acoustic amplitude is obtained for larger
specific heat ratio γ, larger light power absorbed qΦ0L,
smaller beam excitation radius a, and smaller cell volume V0.
Theory cont..
• This equation is valid for near resonance to the lowest radial
mode. For the opposite case of far off-resonance (i.e. non
resonant OA cell), then:
for ω << ω1, i.e. the light beam modulation frequency being
much less than the lowest-radial-mode resonance frequency
 In this nonresonant mode operation (common in OA), the

acoustic amplitude lags behind the beam modulation by 900.
Theory cont..
• Final step of the theory of OA is the detection, which is
frequently done with a microphone.
• If the microphone has a known frequency response, then

all the various components Aj in equation 12 with
frequencies ωj within in the microphone bandwidth will be
detected, and suitable frequency analysis of the
microphone signal should give the various Aj’s.
Theory cont..
• In case of pulsed OA excitation, boundary conditions are frequently
unimportant when short-duration light pulses are used because the time
needed for the acoustic wave to reach the OA cell well is roughly 30
microseconds, which’s much longer than the light pulse duration and
much longer than decay times of excited states in most gases.
• Thus, interference of the generated acoustic wave and the reflected

acoustic waves generally do not occur in contrast to the CW modulated
case.
• However, Pulsed OA generation does produce a “ringing” acoustic signal

due to multiple reflections in the gas cell
Theory cont..
• The net heat released up to time t is:
where W is the total number of photons absorbed
 The pressure increase of the irradiated column of gas

of volume V by using the ideal gas law:
Where R is the universal gas constant, M is the molecular weight, and Cv is the specific
heat per unit mass at constant volume.
Theory cont..
• The time dependence of p(t) for the pulsed OA signal is indicated
in slide 22(b) for the case of short optical pulse duration and long
thermal diffusion time τD, given by
where a is the beam radius and D is the thermal diffusivity of the gas
The initial rise in p(t) depends on the lifetime of the excited

state, while the final slow decrease of p(t) back to zero
depends on the thermal decay time constant τD.
Instrumentation for OA Studies of Gases
Instruments:
• Light source
• OA cell with transducer
• A means of modulating the light source (e.g., pulsing a
laser or using a chopper), or modulating the sample
absorption (e.g., using a modulated electric field for
Stark modulation of the absorption)
Instrumentation:
Two general classes:
Light Source
• Lamps, filament lamps, and glow bars
Inexpensive, usually compact and reliable,

and cover broad spectral ranges from the
UV to the far IR.
Low spectral brightness, incapability of fast
modulation or switching , and necessity of
an external spectral selection element like a
monochromator.
Instrumentation: Light Source
• Lasers
High spectral brightness and collimation, can be

readily modulated by extracavity or by intracavity
means, and are of narrow spectral linewidth.
Expensive and limited tuning range.
Applications
• Measurement of weak Absorption lines
(~10-10cm-1/cell length ~10cm (Patel et al
1977)
• High sensitivity trace detection (SFRL)
• Absorption of excited states
• Chemically reactive gases
• Raman-Gain Spectroscopy (PARS) [non-
linear]
• The nephelometer is an instrument that
measures aerosol light scattering. It detects scattering
properties by measuring light scattered by the aerosol and
subtracting light scattered by the gas, the walls of the
instrument and the background noise in the detector.
https://gml.noaa.gov/aero/instrumentation/neph_desc.html
Lowcost sensors
How IT Measures Air Quality
PurpleAir sensors use PMS*003 series laser counters to measure particulate matter in real time
(the asterisk ‘*’ represents a number determining the version of the laser counter). Each laser
counter within a pair alternates five-second readings averaged over two minutes. Each laser
counter uses a fan to draw a sample of air past a laser beam. The laser beam is reflected off any
present particles onto a detection plate. The reflection is measured as a pulse by the detection
plate. The length of this pulse determines the size of the particle. The number of pulses determines
the particle count. These particle measurements are used to infer the mass concentrations of
PM1.0, PM2.5, and PM10 for standard indoor and outdoor atmospheric particles.
PurpleAir sensors report real-time data that is updated every two minutes. Since air quality can
fluctuate greatly throughout the day, the real-time PurpleAir AQI reading may appear “high” when
compared to 12-hour averaged AQI data.
PMS*003
PMS5003 is a kind of digital and universal particle concentration sensor, which can be used to obtain the
number of suspended particles in the air, i.e. the concentration of particles, and output them in the form of
digital interface. This sensor can be inserted into variable instruments related to the concentration of
suspended particles in the air or other environmental improvement equipments to provide correct
concentration data in time.
Working principles Laser scattering principle is used for such sensor, i.e. produce scattering by using laser to
radiate suspending particles in the air, then collect scattering light in a certain degree, and finally obtain the
curve of scattering light change with time. In the end, equivalent particle diameter and the number of
particles with different diameter per unit volume can be calculated by microprocessor based on MIE theory.
Please find the functional diagram of each part of sensor from Figure 1 as follows.
https://www.aqmd.gov/docs/default-source/aq-spec/resources-page/plantower-pms5003-manual_v2-3.pdf
PMS*003
Low-cost sensors
What PurpleAir Sensors Measure
At this time, PurpleAir sensors measure particulate matter between 0.3μm and 10μm in diameter.
They also measure the temperature, humidity, and pressure of the sensor. Additionally, some of our
sensors include Bosch BME680/688 sensors that measure volatile organic compounds (VOC)
emitted as gases. The readings from this sensor are in an experimental phase at PurpleAir. Further
details about the BME680 are available from the
https://cdn-shop.adafruit.com/product-
files/3660/BME680.pdf?fbclid=IwAR0tr5flhuRuhmM_U_FUH1lQhGdLnRzsFl-
qJC0agspscMbk31afZQ0ECs8
Light Sources
Radiation sources- Lasers, and light sources

basic principles
Lasers
• Laser is the acronym of Light Amplification by Stimulated
Emission of Radiation.
• A device which produces light with a narrow spectral width. Laser
is light of special properties, light is electromagnetic (EM) wave in
visible range.
• A laser is a cavity that has mirrors at the ends and is filled with
lasable material such as crystal, glass, liquid, gas, or dye.
• These materials must have atoms, ions, or molecules capable of
being excited to a metastable state by light, electric discharge, or
other stimulus.
• The transition from this metastable state back to the normal
ground state is accompanied by the emission of photons which
form a coherent beam.
Introduction
• In thermal equilibrium the ratio of (nondegenerate) upper- and lower-state populations
of an atomic or molecular transition is
• In order to have a population inversion on a transition, therefore, the

level populations N2 and N1 must have a non-thermal distribution.
Laser construction
Laser construction
Laser cavity. The electromagnetic wave travels back and forth
between the mirrors, and the wave is amplified with each pass.
The output mirror is partially transparent to allow only a fraction
of the beam to pass out of the cavity.
Laser construction
(a) Energy-level diagram illustrating the principle of operation of a
laser. (b) Basic components of a laser. The population inversion is
created in the lasing medium. Pump energy might be derived from
intense lamps or an electric discharge.
ELECTRON-IMPACT EXCITATION
• A common means of pumping gas lasers is an electric discharge, which
may be produced in a gas contained inside a glass tube by applying a
high voltage to electrodes on either side of the tube. Electrons are
ejected from the negative electrode (the cathode) and drift toward the
positive electrode (the anode). When an electron collides with an atom
(or molecule), there is some probability that the atom makes a transition
to a higher energy state.
• The amplification of radiation by stimulated emission
requires a population inversion, and in order to have a
population inversion we must “pump” the medium to
overcome its natural tendency to reach a thermal
equilibrium. The suitability of a material as a laser
medium thus depends, among other things, on how
readily we can force it away from thermal equilibrium
and establish a population inversion.
• Thus, we speak of optically pumped lasers,
electric-discharge lasers, chemical lasers, gas-
dynamic lasers, etc
EXCITATION TRANSFER
• One way for an excited atom to transfer energy to another atom is by
photon transfer: The photon spontaneously emitted by one atom is
absorbed by the other. In this way the first atom drops to a lower level
and the second atom is raised to a higher level, i.e., there is an
excitation transfer between the two atoms.
• Excitation transfer can occur between two species A
and B even if the transitions are not precisely resonant
EXCITATION TRANSFER
• A*+B A +B* + E
• A*+B A +B* - E
He–Ne LASERS
• The He–Ne electric-discharge laser, with its red output beam at 632.8
nm, is one of the most familiar gas lasers. He–Ne lasers can be made to
operate at many other (mainly infrared) wavelengths. Whatever the
operating wavelength, the active lasing species in He–Ne lasers is the
Ne atom. It is excited by the transfer of excitation from He atoms, which
in turn are excited by collisions with electrons.
• The population inversion mechanism in He–Ne lasers thus involves a
combination of electron-impact excitation (of He) and excitation transfer
(from He to Ne).
DYE LASERS
• Liquid dye lasers provide especially interesting examples of
optical pumping, i.e., population inversion by absorption of
radiation illuminating the laser medium. The active molecules in
these lasers are large organic molecules in a solvent such as
alcohol or water. The most useful feature of dye lasers is their
tunability:
• Optical pumping takes the molecule from one of the vibrational-
rotational levels of the ground electronic state (S0) to one of the
vibrational-rotational levels of the first excited singlet electronic state
(S1). The S0 - S1 transition is possible over a broad frequency range
because there is a broad range of vibrational-rotational levels
associated with both S0 and S1
• For although S - T transitions are radiatively forbidden, they may occur
nonradiatively in collisions between molecules. This is called
intersystem crossing
OPTICALLY PUMPED SOLID-STATE
LASERS
• An electric discharge in the Xe gas produces an intense burst of spontaneous emission
lying in a visible spectral range that is absorbed by the laser rod.
Nd Yag
Semiconductor Diode lasers
• A semiconductor laser diode is a device capable of
producing a lasing action by applying a potential
difference across a modified pn junction. This modified
pn-junction is heavily doped and contained within a
cavity thus providing the gain medium for the laser. A
feedback circuit is also implemented in order to control
the amount of current sent to the laser diode.
• This diagram shows a cross section of the inside of the laser diode.
• The L.D. consists mainly of a pn-junction separated by a thin active layer.
• The sides of the L.D. form the mirrors of the cavity and the beam is sent in the two
opposite directions.
• A potential difference creates the pumping action and starts the lasing process.
How do they work?
Here is another look at how the laser diode creates the lasing
action. This diagram clearly shows how the cavity is formed
by cleaving and polishing the ends and roughening the sides.
• S.L.D.s can range in wavelengths such as Red (635-
670 nm) and IR (780, 800, 900, 1,550 nm, etc). Green
(~550 nm), blue (~450 nm), and violet (~400 nm) laser
diodes have been produced in various research labs
but until recently, only operated at liquid nitrogen
temperatures, had very limited life (
Electronic Excitation by UV/Vis Spectroscopy :
UV: IR: Radio waves:
X-ray: valance
core electron molecular Nuclear spin states
excitation electronic vibrations (in a magnetic field)
excitation
Spectroscopic Techniques and
Chemistry they Probe
UV-vis UV-vis region bonding electrons
Atomic Absorption UV-vis region atomic transitions (val. e-)
FT-IR IR/Microwave vibrations, rotations
Raman IR/UV vibrations
FT-NMR Radio waves nuclear spin states
X-Ray Spectroscopy X-rays inner electrons, elemental
X-ray Crystallography X-rays 3-D structure

Spectroscopic Techniques and Common Uses
Quantitative
UV-vis UV-vis region analysis/Beer’s Law
Quantitative analysis
Atomic Absorption UV-vis region Beer’s Law
FT-IR IR/Microwave Functional Group Analysis

Functional Group
Raman IR/UV Analysis/quant
FT-NMR Radio waves Structure determination
X-Ray Spectroscopy X-rays Elemental Analysis
X-ray Crystallography X-rays 3-D structure Anaylysis

DETECTION- Devices
Frequency Scanning Techniques: a few definitions
Emission method: source of light is sample
Absorption method: intensities of a source with and without the sample in place are
compared
Spectrum: a plot of intensity vs. frequency/wavelength
In quantitative analysis:
common to work at 1 wavelength
running a spectrum is an important initial step (to select best conditions)
Regions of Electromagnetic Spectrum-the “colour” of light
Fig. 18-2
Electronic structures of simple molecule
Energy
Excited state
Singlet
S1
T1 Excited state
Vibration states
Triplet
D
Dissociated states
S0 Bond length
Ground state
Interaction between photon and molecule
S0 S1 transition
S1
S1 T1
T1
UV-vis
D
A F
P
S0
IR
S0
Optical spectrophotometer components
Excitation sources
Deuterium Lamp UV Detectors
Tungsten Lamp
UV-vis PMT
Laser X-ray, UV, vis, IR Monochromators
CCD/CID
X-ray tube X-ray Filters
Mercury lamp UV-vis Grating+slit Photodiode
Xenon lamp prism Thermocouple
UV-vis
Silicon carbide globar IR MCT
Flame Pyroelectric detector
Furnaces
Plasmas
Hollow-cathode lamp
What is the advantage and disadvantage?

Light sources Brightness
Line width
What is the important properties of a source?
Background
Black-body radiation for vis and IR but not UV Stability
- a tungsten lamp is an excellent source of black-body radiation Lifetime
- operates at 3000 K
- produces l from 320 to 2500 nm ( How much in cm-1, J, Hz and eV?)
For UV:
- a common lamp is a deuterium arc lamp
- electric discharge causes D2 to dissociate and emit UV radiation (160 – 325 nm)
- other good sources are:
Xe (250 – 1000 nm)
Hg (280 – 1400 nm)
Lasers:
- high power
- very good for studying reactions
- narrow line width
- coherence
- can fine-tune the desired wavelength (but choice of wavelength is limited)
- £££ expensive £££
Sample a source containers:
for UV: quartz (won’t block out the light)
for vis: glass [l 800nm (red) to l 400 nm (violet)]
for IR: NaCl (to or 15384 nm or 650 cm-1)
KBr (to 22222 nm or 450 cm-1)
CsI (to 50000 nm or 200 cm-1)
Best material: diamond, why?

Optical transmission coefficient
Criteria
High transmission
Chemically inert
Mechanically strong
Monochromators
Early spectrophotometers used prisms
- quartz for UV
- glass for vis and IR Why?
These are now superseded by:

http://www.ii.com/images/prism.jpg
Diffraction gratings:
- made by drawing lines on a glass with a diamond
stylus
ca. 20 grooves mm-1 for far IR
ca. 6000 mm-1 for UV/vis
- can use plastic replicas in less expensive
instruments
Think of diffraction on a CD
http://www.mrfiber.com/images/
10mmx10mm cddiffract.jpg
http://www.veeco.com/library/nanotheater_detail.php?type
=application&id=331&app_id=34
Monochromators: cont’d
What is the purpose of concave mirrors?
Polychromatic radiation enters
The light is collimated the first concave mirror
Reflection grating diffracts different
wavelengths at different angles
Second concave mirror focuses each wavelength at

different point of focal plane
Orientation of the reflection grating directs only
one narrow band of wavelengths to exit slit
http://oco.jpl.nasa.gov/images/grating_spec-br.jpg
Interference in diffraction
d sin(q)+d sin(f)=nl
d
Bragg condition
Phase relationship
q>0 f
f<0 q n=1, 2, 3 In-phase
n=1/2, 3/2, 5/2 out-phase
Young’s Double Slit
Interference Experiment
m=2
y m=1
q m=0
m=1
m=2
D
If you now send the light from the two openings onto a screen, an
interference pattern appears, due to differing path lengths from each
source
• we have constructive interference if paths differ by any number of full
wavelengths
• destructive interference if difference is half a wavelength longer or
shorter
Constructive interference Constructive interference Destructive interference

Geometry Path length difference
Constructive interference
Destructive interference
Destructive interference Constructive interference
How do we locate the vertical position of the fringes on the screen?
1) L >> d
2) d >> λ
These tell us that θ is small
Therefore,
Intensity Distribution
The electric field at P is sum of E1 and
E2. However the Poynting vector is
Taking the time average, the intensity I
represents the correlation between the two waves. For

incoherent light, as there is no definite phase relation
between E1 and E2 and cross term vanishes
and incoherent sum is

For coherent sources, the cross term is non-zero. In fact, for constructive
interference E1 = E2 and I = 4I1
For destructive interference E1 = -E2 and and correlation term = - I1, the
total intensity becomes I = I1 -2I1 + I1 = 0
Suppose that the waves emerged from the slits are coherent sinusoidal plane
waves. Let the electric field components of the wave from slits 1 and 2 at P be
given by
We have dropped the kx term by assuming that P is at the origin (x =0) and
we have acknowledged that wave E2 has traveled farther by giving it a phase
shift (ϕ) relative to E1
For constructive interference, with path difference of δ = λ would correspond

to a phase shift of ϕ=2π. This then implies
• Double slit experiment produces interference
pattern if light is coherent
For constructive interference:
For destructive interference:
Intensity:
Newton’s rings are similar, but with curved glass:
Why different colors? for any given difference in path length, the
condition ΔL =n (m+1/2)λ might be satisfied for some wavelength but
not for some other. A given color might or might not be present in the
visible image.
Pass around Newtons Rings
Diffraction
In his 1704 treatise on the theory of optical phenomena (Opticks), Sir Isaac
Newton wrote that "light is never known to follow crooked passages nor to
bend into the shadow".
He explained this observation by describing how particles of light always

travel in straight lines, and how objects positioned within the path of light
particles would cast a shadow because the particles could not spread out
behind the object.
True, to a point.
On a much smaller scale, when light waves pass near a

barrier, they tend to bend around that barrier and spread at
oblique angles.
This phenomenon is known as diffraction of the light, and

occurs when a light wave passes very close to the edge of an
object or through a tiny opening, such as a slit or aperture.
Diffraction is a wave effect
Interference pattern of light and dark bands around

the edge of the object.
Diffraction is often explained in terms of the Huygens

principle, which states that each point on a wavefront
can be considered as a source of a new wave.
All points on a wavefront serve as point

sources of spherical secondary wavelets.
After a time t, the new position of the
wavefront will be that of a surface
tangent to these secondary wavefronts
Diffraction by a Single Slit - Locate the First Minima
D >> a, rays are parallel

Divide the screen into two zones of width a/2
Find the first minima above the midpoint by pairing
up rays from the top point of the top zone and the top
point of the bottom zone
Rays are in phase at the slit but must be out of phase

by by λ/2 at screen
The path length difference = a/2 sin θ

Repeat for other pairs of rays in the upper zone and
lower zone: a/2 sin θ = λ/2
a sin θ = λ first minima
If we narrow the slit the angle must get bigger

- more flaring - - what happens when a = λ?
Diffraction by a Single Slit - Subsequent
Minima
Repeat the process for paired rays (4) from
corresponding points from each of the zones
Rays are in phase at the slit but must be out of phase

by by λ/2 at screen
second minimum
Dark fringes - minima

Intensity in Single Slit Diffraction - Derive using
phasors - see text alpha
where
α is just a convenient connection between the angle θ that locates a point on

the screen and the light intensity I(θ)
I = Im occurs at the central maximum (θ = 0) and ϕ is the phase difference (in

radians) between the top and bottom rays from the slit of width a
Studying the expression above reveals that the intensity minima occur at
Plug this into the expression for α above and we find

Diffraction by a circular aperture (lens ...)
When light from a point source
passes through a small circular
aperture, it does not produce a
bright dot as an image, but rather a
diffuse circular disc known as Airy's
disc surrounded by much fainter
concentric circular rings. This
example of diffraction is of great
importance because the eye and
many optical instruments have
circular apertures.
A complex analysis leads to First minimum
Compare to the relation for a single slit

Resolvability
The fact that a lens image is a diffraction pattern is important when trying to
resolve distant point objects
When the angular separation for two objects is such that

the central maximum of one diffraction pattern coincides
with the first minimum of the other we have a condition
called the Rayleigh’s criterion for resolvability
Diffraction Gratings Like the double slit arrangement but with a
much greater number of slits, or rulings,
sometimes as many as several 1000 per
millimeter
Light passed through the grating forms

narrow interference fringes that can be
analyzed to determine the wavelength
As the number of rulings increases beyond 2

the intensity plot changes from that of a
double slit pattern to one with very narrow
maxima (called lines) surrounded by relatively
wide dark regions
Diffraction Gratings
Principal maxima, where all waves interfere
constructively are found with what is now a
familiar procedure:
each m represents a different line and the

integers are called order numbers
Rewriting the above we find
So the angle to a particular line (say m =3) depends on the wavelength being
used
Dispersion
In order to distinguish different wavelengths that are close to each
other a diffraction grating must spread out the lines associated with
each wavelength. Dispersion is the term used to quantify this and is
defined as
Δθ is the angular separation between two lines that differ by Δλ. The
larger D the larger the angular separation between lines of different λ.
and D gets larger for higher order

It can be shown that (m) and smaller grating spacing
(d)
Resolving Power
To make lines that whose wavelengths are close together (to resolve them)
the line should be as narrow as possible
The resolving power is defined by
where λavg is the average of the two wavelengths studied and Δλ is the difference
between them. Large R allows two close emission lines to be resolved
To get a high resolving power we

It can be shown that
should use as many rulings.
Dispersion and Resolving Power
Three gratings illuminated with light of
λ=589 nm, m = 1
Grating N d(nm) θ D(o/μm) R
A 10000 2540 13.4 23.2 10000 Highest resolution
B 20000 2540 13.4 23.2 20000
C 10000 1360 25.5 46.3 10000
Highest dispersion
Another look at Monochromators
• The many grooves, which are illuminated coherently, can
be regarded as small radiation sources, each of them
diffracting the light incident onto this small groove with a
width d ≈ λ into a large range Δr ≈ λ/d of angles r around
the direction of geometrical reflection. The total reflected
light consists of a coherent superposition of these many
partial contributions.
• Only in those directions where all partial waves emitted
from the different grooves are in phase will constructive
interference result in a large total intensity, while in all
other directions the different contributions cancel by
destructive interference.
Another look at Monochromators
At an angle of incidence α to the grating normal (which is normal to

the grating surface, but not necessarily to the grooves) one obtains constructive
interference for those directions β of the reflected light for which the path
difference Δs =Δs1−Δs2 is an integer multiple m of the wavelength λ. With
Δs1 = d sin α and Δs2 = d sin β this yields the grating equation
d(sin α° + sin β) = mλ ,
the plus sign has to be taken if β and α are on the same side of the grating
normal; otherwise the minus sign, which is the case
• The reflectivity R(β, θ) of a ruled grating depends on the diffraction angle β and on the
blaze angle θ of the grating, which is the angle between the groove normal and the
grating normal . If the diffraction angle β coincides with the angle r of specular reflection
from the groove surfaces, R(β, θ) reaches its optimum value R0, which depends on the
reflectivity of the groove coating.
• α and β are on opposite sides of the grating normal, i = α−θ and r = θ+β, which
yields, for specular reflection i = r, the condition for the optimum blaze angle θ
θ = (α−β)/2 .
• Because of the diffraction of each partial wave into

a large angular range, the reflectivity R(β) will not have a sharp maximum
at β = α−2θ, but will rather show a broad distribution
around this optimum angle. The angle of incidence α
is determined by the particular construction of the
spectrometer, while the angle β for which constructive
interference occurs depends on the wavelength λ.
Therefore, the blaze angle θ has to be specified for
the desired spectral range and the spectrometer type.
• In laser-spectroscopic applications the case α = β often occurs, which
means that the light is reflected back into the direction of the incident
light. For such an arrangement, called a Littrow-grating mount
• the grating equation for constructive interference reduces to

2d sin α = mλ .
• Maximum reflectivity of the Littrow grating is achieved for i =r =
0→θ = α The Littrow grating acts as a wavelength-selective
reflector because light is only reflected if the incident wavelength
satisfies the condition
SIGNAL TO NOISE RATIO
• Ratio of the diffracted energy to unwanted light energy.
The above mentioned characteristics depend on the following

parameters of the grating.
1. Groove profile
2. Groove frequencies
3. Groove pattern
4. Substrate shapes
5. Surface irregularities
And these parameters depend on the method of manufacturing :

Ruled Gratings or Holographic Gratings
Efficiency characteristics
• Absolute efficiency is the ratio of the diffracted light to the energy of
the incident light.
• Relative efficiency is the ratio of the energy of the diffracted light to
the energy from the light reflected from a polished surface.
• Blazing is the control over the magnitude and variation of diffracted
energy with the change in wavelength. This control is generally
obtained by getting control over the blazing angle or the groove
angle.
θ
α
θ
Detection of Light
• For many applications in spectroscopy the sensitive detection
of light and the accurate measurement of its intensity are of
crucial importance for the successful performance of an
experiment. The selection of the proper detector for optimum
sensitivity and accuracy for the detection of radiation must
take into account the following characteristic properties,
which may differ for the various detector types:
• The spectral relative response R(λ) of the detector,

which determines the wavelength range in which the
detector can be used. The knowledge of R(λ) is essential
for the comparison of the true relative intensities I(λ1) and
I(λ2) at different wavelengths.
Detection of Light
• The absolute sensitivity S(λ) = Vs/P, which is defined as the
ratio of output signal Vs to incident radiation power P. If the
output is a voltage, as in photovoltaic devices or in
thermocouples, the sensitivity is expressed in units of volts
per watt. In the case of photocurrent devices, such as
photomultipliers, S(λ) is given in amperes per watt. With the
detector area A the sensitivity S can be expressed in terms of
the irradiance I :
S(λ) = Vs/(AI ) .
Detection of Light
• The achievable signal-to-noise ratio Vs/Vn, which is, in principle, limited by the
noise of the incident radiation. It may, in practice, be further reduced by inherent
noise of the detector. The detector noise is often expressed by the noise equivalent
input power (NEP), which means an incident radiation power that generates the
same output signal as the detector noise itself, thus yielding the signal-to-noise
ratio S/N = 1. In infrared physics a figure of merit for the infrared detector is the
detectivity
• The detectivity D∗ [cm s−1/2 W−1] gives the obtainable signal-to-noise ratio
Vs/Vn of a detector with the sensitive area A =1 cm2 and the detector
bandwidth Δ f = 1 Hz, at an incident radiation power of P = 1W. Because
the noise equivalent input power is NEP = P °Vn/Vs, the detectivity of a
detector with the area 1 cm2 and a bandwidth of 1 Hz is D∗ = 1/NEP.
Detection of Light
The maximum intensity range in which the detector response
is linear. It means that the output signal Vs is proportional to
the incident radiation power P. This point is particularly
important for applications where a wide range of intensities is
covered. Examples are output-power measurements
of pulsed lasers, Raman spectroscopy, and spectroscopic
investigations of line broadening, when the intensities in the
line wings may be many orders of magnitude smaller than at
the center.
Detection of Light
• The time or frequency response of the detector, characterized by its time constant τ.
Many detectors show a frequency response that can be described by the model of a
capacitor, which is charged through a resistor R1 and discharged through R2 . When a
very short light pulse falls onto the detector, its output pulse is smeared out. If the
output is a current i(t) that is proportional to the incident radiation power P(t) (as,
for example, in photomultipliers), the output capacitance C is charged by this
current and shows a voltage rise and fall, determined by
• If the current pulse i(t) lasts for the time T, the voltage V(t) at the capacitor
increases up to t = T and for R2C >> T reaches the peak voltage
which is determined by C and not by R2!

Detection of Light
• After the time T the voltage decays exponentially with the time constant τ
=CR2. Therefore, the value of R2 limits the repetition frequency f of pulses to f
< (R2C) −1. The time constant τ of the detector causes the output signal to rise
slower than the incident input pulse. It can be determined by modulating the
continuous input radiation at the frequency f . The output signal of such a
device is characterized by
• where τ = CR1R2/(R1+ R2). At the modulation frequency f = 1/(2πτ), the

output signal has decreased to 1/ √2 of its dc value. The knowledge of
the detector time constant τ is essential for all applications where fast
transient phenomena are to be monitored, such as atomic lifetimes or
the time dependence of fast laser pulses
Detectors : Radiation-----charger converter
Choice of detector depends upon what wavelength you are studying
Want the best response for the wavelength (or wavelength range) that you are studying
In a single-beam spectrophotometer, the 100% transmittance control must be adjusted
each time the wavelength is changed
In a double-beam spectrophotometer, this is done for you!
Photomultiplier-single channel, but very high sensitivity
- Light falls on a photosensitive alloy

(Cs3Sb, K2CsSb, Na2KSb)
- Electrons from surface are
accelerated towards secondary
electrodes called dynodes and
gain enough energy to remove
further electrons (typically 4-12,
to 50 with GaP).
- For 9 stages giving 4 electrons for

1, the amplification is 49 or 2.6 x
105)
- The output is fed to an amplifier

which generates a signal
- To minimise noise it is necessary to
operate at the lowest possible
voltage
What decide the sensitive wavelength?

Photodiode Array-multiplex, but low sensitivity
Good for quick (fraction of a second) scanning of a full spectrum

Uses semiconductor material:
Remember: n-type silicon has a conduction electron – P or As doped
p-type silicon has a ‘hole’ or electron vacancy – Al or B doped
A diode is a pn junction:
under forward bias, current flows from
n-Si to p-Si
under reverse bias, no current flows
boundary is called a depletion layer or
region
Photodiode Array
- Electrons excited by light partially discharge the condenser
- Current which is necessary to restore the charge can be detected
- The more radiation that strikes, the less charge remains
- Less sensitive than photomultipliers  several placed on placed on single crystal
- Different wavelengths can be directed to different diodes
- Good for 500 to 1100 nm
- For some crystals (i.e. HgCdTe) the response time is about 50 ns
Could you compare photodiode with CCD detector?

Photodiode Array Spectrophotometer
- For photodiode array spectrophotometers, a white light passes through sample
- The grating polychromator disperses the light into the component wavelengths
- All wavelengths are measured simultaneously
- Resolution depends upon the distance between the diodes and amount of dispersion
No moving parts!
Simple mechanical and optical design, very compact.
Photodiode Array Spectrophotometers
vs Dispersive Spectrophotometers
Dispersive Spectrophotometer:
- only a narrow band of wavelengths reaches the detector at a time
- slow spectral acquisition (ca. 1 min)
- several moving parts (gratings, filters, mirrors, etc.)
- resolution: ca. 0.1 nm
- produces less stray light  greater dynamic range for measuring high absorbance
- sensitive to stray light from outside sources i.e. room light
Photodiode Array
Spectrophotometer:
- no moving parts  rugged
- faster spectral acquisition (ca.
1 sec)
- not dramatically affect by
room light
What are the components 1 to 10?

From: http://www.oceanoptics.com/
Property of luminescence spectrum
Fluorescence vs phosphorescence
1. Phosphorescence is always at longer wavelength compared with fluorescence

2. Phosphorescence is narrower compared with fluorescence
3. Phosphorescence is weaker compared with fluorescence
Why?
Absorption vs emission
1. absorption is mirrored relative to emission

2. Absorption is always on the shorter wavelength compared to emission
3. Absorption vibrational progression reflects vibrational level in the electronic
excited states, while the emission vibrational progression reflects vibrational
level in the electronic ground states
4. l0 transition of absorption is not overlap with the l0 of emission
Why?
Fluorescence spectroscopy
Fluorescence spectroscopy
Light source Beam
splitter Q: why the emission is
Excitation measured at 90 relative to
monochromator
sample the excitation?
Emission
Monochromator
Reference
diode
PMT Amplifier Computer
Emission spectrum: hold the excitation wavelength steady and measure the emission at
various wavelengths
Excitation spectrum: vary the excitation wavelength and vary the wavelength measured
for the emitted light
Photomultiplier Tube
What is it?
• Extremely sensitive detector of light in the ultraviolet,
visible and near infrared
• Multiplies the signal produced by incident light by as
much as 108
– single photons can be resolved
• High gain, low noise, high frequency response, and
large area of collection
• A tiny and normally undetectable current becomes a
much larger and easily measurable current
Vs. Phototube
• In both, the photon strikes the photocathode and emits
electrons (photoelectric effect)
• In a phototube only these few electrons are collected
– It can only be used for very low signals
• In a photomultiplier tube these electrons are multiplied
– This process is called secondary emission
Components
• Made of a glass vacuum tube
• Photocathode
• Several dynodes
• One anode
How it works
How it works
 Electron is released by the photocathode
 Electron is then multiplied by the electrodes
 Metal channel dynodes
 At the end of the chain is the collection electrode
 Anode
 The current flowing from the anode to ground is
directly proportional to the photoelectron flux
generated by the photocathode
Dynodes
• Each is held at a more positive voltage than the
previous one
• As the electron approaches the dynode, it is
accelerated by the electric field
• On striking it, more low energy electrons are emitted
and accelerated to the next dynode in the series
Anode
• The final electrode in the chain of dynodes
• The electrons accumulate here
• This charge results in a sharp current pulse indicating
the arrival of a photon
The Variables
• Photocathode thickness
– Too thick and more photons will be absorbed, less
electrons will be emitted
– Too thin and too many photons will pass through without
being absorbed
• Semitransparent Photocathode
– Multiplies the electrons to up to 100 million
•
Usage
Require 1000 to 2000 volts
– Negative voltage is connected to cathode and
the positive to the anode
– Distributed to the dynodes by a resistive
voltage divider (series of resistors)
• Must be shielded from ambient light
– To prevent destruction through over excitation
• If used in an area of high magnetic fields it
must be shielded by a layer of mu-metal
– Mu-metal is a nickel-iron alloy with a very high
magnetic permeability
Photodetectors

Unit 7-Instrumentation Optical Measurments.

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ASM-804 Advanced

Atmospheric Chemistry and Air Quality

– Rotational transition: far-IR (20-100 mm)

Divisions arise because of different optical materials and

1.) Infrared (IR) spectroscopy: based on IR absorption by molecules as undergo

Interatomic Distance (r)

Potential energy resembles classic Harmonic Oscillator

3.) Typical IR spectrum for Organic Molecule

Bond Stretching Bond Bending

symmetric In-plane rocking

asymmetric In-plane scissoring

Out-of-plane twisting In-plane rocking Out-of-plane wagging

2) CO2: 3(3)-5 = 4 modes

- + - moving in-out of plane

The frequency of the asymmetric stretching vibration in CO2 is at a

2. Qualitative analysis – simple, fast, nondestructive

Simplified diagram of a double beam infrared spectrometer

The techniques and applications of near-infrared (NIR) and

Near-infrared: 0.8 -2.5 mm, 12500 - 4000 cm-1

Where; A = Absorbance a = Extinction coefficient for photon-absorbing

Primary fluorescence- intrinsic property of a substance

1. laser strikes fluorophore

Light is collected CCDs or PMTs

2- Excited State Lifetime: Energy

3- Fluorescence Emission: Photon of

• Emission filters are selected to

• Spectral bandwidth of dyes (need to isolate them)

• Spectral overlap when multiplexing

• SO2 + hn214nm  SO2*

• Chemiluminescence is the generation of light by a chemical

An Anglerfish trying to make a

The definition of the aerodynamic

W. Lindsley, B. Green, F. Blachere, S. Martin, B. Law,

Condensation Particle Counters

• Saturate an aerosol with water or alcohol vapor

VTE-Terminal electrostatic velocity

A charged particle will be pushed in the direction of VTE by the

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Efficiently size-selects charged

  Absorption (Extinction) Coefficient

• Light introduced and detected through a mirror rather than through a

• Light intensity inside of the optical cavity depends on a number of

• Path length is no longer a well-defined quantity !

• So …. offers potential for very high sensitivity absorption (or extinction)

After m roundtrips the power would have decreased to

After m-rounds the power has decreased to:

Pm  (Re LA ) 2 m P1  [(1  T  A)e LA ]2 m P1

record an exponential decay with decay time, defined as

The differential cavity loss is therefore

Minimum detectable absorption is limited by the

 ext (l )   ab ,aero (l )   scat , aero (l )   ab, gas (l )   scat , gas (l )

• Mode broadening occurs ass ∆t becomes smaller than tR

Net Result: Passive coupling between laser and cavity

• Measurements of small absorption cross sections

• Laboratory chemical kinetics

• Laboratory measurements of radicals - e.g., photochemistry

• Field measurements I - Atmospheric trace gas detection

• Field measurements II - Aerosol extinction

ABCD ray matrices Represent propagation through optical elements

Ray path A thin lens with focal length f

Propagation through a distance d in a z1 z2

Reflection from a Spherical mirror of Radius R

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