Lasers and Scattering

Lectures in Optical Flow and Combustion Diagnostics

Outline
Quantum Mechanics
Wave Mechanics
Statistical Mechanics
Lasers
Fundamentals
Types of lasers
Scattering
Mie scattering
Point measurements for species and temperature
Rayleigh scattering
Raman scattering
CARS

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Basics of Quantum Mechanics

Light quanta (photon): E = h (Einstein)
h => Plancks constant
Hydrogen atom (Bohr)
Electron orbit is quantized
Change from one orbit to another involves E
Quantization rule: pi dqi = ni h (Sommerfeld)
Wave-particle duality: 2r = n (de Broglie)
Wave equation of particle motion (Shrdinger)
Wave function is related to probability density distribution
(Born)
Uncertainty principle (Heisenberg)
Finite breadth of spectral transitions (frequency spread)
Very small
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Atomic spectroscopy
Multi-electron systems: exclusion principle (Pauli)
4 quantum numbers: n, l, ml, ms; l: s, p, d, f, g
No two electrons in an atom shall possess the same set of
quantum numbers
Leads to multiple states (configurations) in which the system
can exist
Implies plausible transition between any two of the multiple
states
Optical frequency of radiative transitions between
configurations
nm = (En Em) / h (Planck)
Transitions do not occur between all states: selection rules
Spectroscopy is basically a set of rules governing the allowable
configurations, configurational changes, and energies
associated with these changes
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Molecular spectroscopy
Molecular spectra lot more complicated!
Molecules can rotate and vibrate
Three modes of excitation: electronic, rotational, vibrational
Additional quantum numbers: J and v
Transitions can occur in which any one, two, or all three modes
change
Vibration-rotation interaction
Important in Raman spectroscopy
Vibrational states spread out due to rotational interaction
Higher the rotational state, greater the spread
Higher rotational states are more populated at higher temperature
Electronic modelling
United atom or separated atom approach: new quantum number
Multi-electron systems; degeneracy
Rotational-electronic interaction
Selection rules
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Line broadening
Transitions possess finite frequency breadth (linewidth)
Natural linewidth (small) due to uncertainty principle
Doppler broadening
Atoms/molecules are always in thermal motion
Radiation from molecule towards observer appears at higher
frequency and vice versa (Doppler effect)
Velocity variation of atoms/molecules given by Maxwellian
distribution
broadening of spectral lines (Guassian)
Centre frequency gets Doppler-shifted also
Important at low pressure (low collisional broadening) and high
temperature
Pressure (collisional) broadening
Molecular interaction with radiation interrupted by collisions
Leads to broadening of spectral lines (Lorentzian, broader)
At ~STP, pressure broadening dominates Doppler broadening
At elevated temperature, they are comparable

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Statistical mechanics
In an ensemble of molecules, different molecules are
populated/partitioned in different states at a given
temperature according to the Boltzmanns distribution
Spectroscopic diagnostic techniques measure these population
distributions and from them infer the temperature and
concentration at the measurement location

Rotational and vibrational population distributions are quite

temperature sensitive
Leads to laser diagnostic signatures that are quite temperature
dependent

Underlying basis for spectroscopic thermometry

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Radiative interactions/diagnostic signatures

Spontaneous emission
Atom or molecule in an upper or excited state may transition to a
lower energy level by emitting a photon
Absorption
Loss of irradiance due to energy absorbed for the same transition
Intensity of absorption (change in irradiating intensity) depends
on width of absorbing medium
Line-of-sight integrated effect
Stimulated emission
In the presence of radiation, an atom or molecule could be
stimulated to emit radiation (Einstein)
These interactions form the basis for both formation of laser
radiation as well as response to combustion species to laser
radiation
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Lasers
Light Amplification by Stimulated Emission of Radiation
We would like to regard lasers as black boxes
so long as it works to specifications!
Emits a collimated beam of light of the right frequency breadth,
power, time duration, repetition rate, beam profile, etc.
So, need to have knowledge of laser specifications and their
significance
Different laser classifications
Continuous wave (CW) lasers
Pulsed lasers
Freely pulsed
Q-switch pulsed
Solid state lasers
Liquid/dye lasers
Gas lasers

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

General schematic of laser

cavity mirrors

light
output
active medium

R = 100% excitation means R < 100%

back mirror partial mirror

Active medium contains species that is actually lased

Mixture of several constituents, gaseous, liquid or solid form
Excitation means can be by electrical discharge, chemical reaction,
or visible radiation pumping (laser or flashlamp)
Partial mirror is of spatially varying reflectivity in modern systems

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Population inversion
Boltzmann statistics apply at equilibrium
Successively higher energy states are progressively less populated
Interaction of radiation with matter at thermal equilibrium
results in absorption being larger than stimulated emission
For laser action, non-equilibrium situation needs to be created
Stimulated emission must exceed absorption for amplification
A higher population at an upper state than lower state is called
population inversion
Such a situation is created by an external means of excitation

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Four level system

4 collisional and
spontaneous
decay
3 stimulated (lasing)
excitation and spontaneous
2 decay

1
Population inversion cannot be produced in a two-level system
In a 4-level system, level 2 can be sufficiently above level 1 so
as to have little population
Population inversion occurs between levels 3 and 2
Desirable to have (3 2) (4 1)
Quantum efficiency = (3 2) / (4 1)
Fundamental upper limit on overall lasing efficiency

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Optical cavities and cavity modes

Stimulated emission is radiated in the same direction as the
stimulating radiation
Directionality and power provided by optical cavities
Repeated reflections at the cavity mirrors leads to extraction
of significant fraction of energy stored in the inversion
Optical power is extracted from the cavity by having one of
the mirrors partially transmitting
Optical cavity permits only certain discrete modes to be
amplified
Mode spacings are usually smaller than the linewidth of lasing
transitions

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Cavity transverse modes

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

TEM00
Transverse modes are also possible, involving
intermediate node lines and anti-phase oscillations in
the beam profile for higher harmonics of transverse
modes
TEMxy stands for transverse electric mode with index
X and Y denoting mode shapes
Index 00 stands for fundamental mode without intermediate
node lines
TEM00
lowest order transverse mode; most commonly
used
Uniform phase beam profile with Gaussian intensity distribution

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Q-switching
Very energetic pulses are created by this technique
Need to create and store large population inversion
Population inversion is diminished by the lasing action itself
Power loss is artificially created by some means, e.g., Pockels cell
When large inversion is built up, resonance is restored, leading to
intense lasing in a very short period
Q is a measure of the ratio of energy stored to the power loss
With power loss created, Q is initially held down; then turned up
=> Q switching
Pockels cell changes the polarization momentarily and prevents
reflection
polarizer

Pockels cell flashlamp and active medium

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Frequency doubling/tripling/quadrupling
A second harmonic (2) generator is a non-linear crystal
used for doubling the frequency (or halving the wavelength)
Typically needed for Nd:YAG lasers which operate at a
fundamental frequency of 1064 nm (IR) to obtain visible green
light at 532 nm
Phase matching
Crystal is oriented such that the direction of propagation of the
pump beam is at a specific angle to the crystal axis
Can be tuned for maximizing power
Most commonly used crystal: potassium dideuterium phosphate
(KD2PO4 or KD*P)
Third harmonic (3) and fourth harmonic (4) also
available
3 (355 nm) used for CH2O-PLIF
4 (266 nm) used for acetone-PLIF

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Nd:YAG laser

Trivalent neodymium ions Nd3+ housed in Yttrium-Aluminium-
Garnet (Y3Al5O12) crystalline host material
Flashlamp or diode-pumped (usually flashlamp-pumped)
Nd3+ can be housed in glass also, but YAG permits both CW and
pulsed operation at high repetition rate
We use pulsed operation at ~20 Hz repetition rate
Q-switched pulsed operation
For double pulse, usually twin-resonator system is used,
although Q-switching can be done to obtain two pulses with a
single resonator
Dichoric mirror used for beam alignment with twin resonator
YAG rods: 1 cm dia and 10 cm long
0.5% conversion efficiency from flashlamp energy to 1064 nm
laser output
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Twin Nd:YAG laser lay-outs 1

Telescopic resonators

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Twin Nd:YAG laser lay-outs 2

Critical resonators

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Typical Nd:YAG laser specifications

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Dye laser

Most lasers yield fixed frequencies, due to the discrete atomic
states in the active medium
Complex organic molecules (dyes) possess large number of
closely packed vibrational-rotational transitions
E.g., molecule with ~50 atoms involves ~150 modes
Emission from dyes can be continuously tuned over a range
E.g., Coumarin, pyridene, fluorescein, rhodamine B, 6G, etc.
Emission lasing bandwidth extremely narrow
E.g., 10-2 cm-1; extremely fine spectral resolution
Most dye lasers are pumped by another laser, say, Nd:YAG laser
Laser-pumped dye lasers generally possess better beam quality and
spectral characteristics: narrower linewidth, better frequency
stability, etc.
Typically used for LIF applications

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Ruby laser

Historical importance: first used to develop laser action
Trivalent chromium ions, Cr3+ hosted by crystalline Al2O3
Flashlamp excited
Ruby rod 1 cm dia, 10 cm length (~same as Nd:YAG)
3-level system; overall efficiency ~ 0.1%
Need intense pumping
Radiation @ 694.3 nm (room temperature)
Not very useful in diagnostics
not optimum for pumping dye lasers also
Can be operated in CW or Q-switched
CW: freely run, pulsing in short duration spikes for 100 m
Pulsed: power of ~1-10 J per pulse; rep. rate: a few pulses a min.

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Copper vapour laser

510.6 nm (~green) and 578.2 nm (~yellow)
Discharge-excited copper vapour
Unlike other lasers requiring cooling, Cu vapour laser is
insulated in a ceramic cavity
Required to maintain temperature at 1500 C
Most efficient gas laser in the visible spectrum
Power: 100s of J 10 mJ per pulse
Rep. rate: > 1000 Hz
Pulse width ~ 10s of ns
Useful for instantaneous high-speed flow visualization
Can also be used for PIV
Difficult with low energy per pulse

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Excimer laser

Uses for active medium, an excited state complex or exciplex
i.e., A + B*
(AB)* is stable, but AB is not
Typical exciplexes are rare gas dimers and rare gas halides
E.g., Ar2, Xe2, KrF, XeCl, etc.
Intense pumping using electron beams/electric discharge
High quantum efficiency, but low overall efficiency
~1% (high) in lab and < 0.1% in commercial systems
ArF: 193 nm, KrCl: 222 nm, KrF: 249 nm, XeCl: 308 nm, XeF:
353 nm
~1 J/pulse at low rep. rate, or ~ kHz rep. rate at low energy

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Helium-neon laser

First gas laser, first CW laser
Atomic levels of neon pumped by energy transfer from long-
lived meta-stable states of He excited in an electric discharge
632.8 nm (red)
0.1-10 mW power
Coherence and Gaussian profile at TEM00
Commonly available
Used for some small-scale diagnostics

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Lasers: Argon ion laser

CW laser action by Ar+ ions
Mainly 514.5 and 488 nm lines
~10 W possible in single line at TEM00
Efficiency of ~0.1%
Useful for low-speed PIV (water), LDV, PDPA, Rayleigh
scattering, etc.

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Light interaction with flow medium

flow medium emission
light

absorption scattering

elastic inelastic

Mie scattering Rayleigh Raman Fluorescence

(1871) (1928)
particle
level molecular level

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Absorption, Emission, and Scattering

Absorption provides measurements averaged over a path
Not strictly a point measurement
Deconvolution possible in some cases
We dont concern ourselves with absorption based techniques
Emission measurements also are integrated along the line-of-
sight
E.g., chemiluminescence of CH*, OH*, etc.
Line-of-sight integration can be corrected for in 2-D geometry
Easier to measure
Scattering
Elastic scattering involves no change in and vice versa
When particle d >> , we have Mie scattering
Mie scattering extensively useful in LDV, PDPA, PIV, and
concentration measurements
Rayleigh, Raman, and fluorescence useful in temperature and
species concentration measurements

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Scattering
Scattering is the re-direction of light caused by its interaction
with particles
Particles of different kinds (molecular or macroscopic) in the
flow field exhibit a wide range of scattering signals, besides
emission, and incident radiation after absorption
Compton
flow Bragg
Brillouin
incident
light Rayleigh

Raman
Mie fluorescence
Mie scattering overwhelms other scattering signals when
large particles are present
Rayleigh, Raman, etc. can be effectively observed mainly in
clean flows/combustion, i.e., without particulate matter

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Mie Scattering
For visible light, ~ 0.5 mm, particles with d 1 m most
prominently exhibit Mie scattering
Mie scattering does not involve the energy levels of the
particles molecules
All wavelengths are scattered
The chief mechanism is that the electric and magnetic fields
are slightly altered around the particle, resulting in a radiation
field produced by the particle
Geometrical optics does not adequately describe this process
Need Mie theory rigorous optical theory
Mie scattering intensity depends on
Incident beam intensity
Particle size (greater the size, greater the intensity)
Wavelength
Direction with respect to the incident beam

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Directionality of Mie scattering

Mie scattering is highly directional
Reflections off a spherical particle act as point sources, and some
sort of interference occurs from these sources, leading to lobes of
high and low intensity
Forward scatter is the strongest
Backward scatter is relatively weak
Sideways is the worst

incident beam

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Particles to seed for Mie Scattering

Mie scattering is used in both qualitative flow visualization and
quantitative diagnostic techniques
Particles should follow the flow and at the same time, d >>
Particle sizes are typically in the range of 1-10 m (for ~ 0.5 m)
Stokes number very small
Typical tracer particles used are
Olive oil aerosols
Ethanol
Alumina
Titania (particulate or reactive formation of TiCl4 with moisture)
Water droplets (atomized or condensed from steam)
Neutral density particles such as hollow glass spheres in water flows
Particle concentration should not be too high to impede the flow
Volume fraction < 10-5 (one-way interaction)

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Rayleigh, Raman, and fluorescence

Point measurements

Rayleigh Raman Fluorescence

Anti-Stokes Stokes
Raman laser Raman laser

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Rayleigh and Raman scattering

r relatedrto the incident electric field
Induced dipole moment is
p = 0 E
where, is the polarizability
Let polarizability be expanded as a sum of a fixed term and a
derivative w.r.t. to a normal coordinate Q

= 0 + Q
Q 0
If Q oscillates at some natural frequency of the medium
Q = Q0 cos t
with incident wave at frequency 0
Anti-
Stokes Stokes
r r
p = 0 + Q0 cos t 0 E0 cos 0t Raman Raman
Q 0
r
r Q E
= 0 0 E0 cos 0t + 0 0 0 [cos( 0 )t cos( 0 + )t ]
Q 0 2
Rayleigh
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Rayleigh scattering
The molecules return to the same state after interaction with
the incident light quanta
Scattered light has the same frequency as the incident light
(elastic scattering)
Scattered signal is not specific to any particular species
Total density measurement can be performed, but individual
species concentration cannot be performed
Temperature measurement
Using the perfect gas law, at constant pressure
Resolving Doppler linewidth of the scattering signal
Can be done when pressure broadening does not dominate
Signal intensity stronger than other molecular spectroscopic
signals, but less than Mie scattering signal
Needs to be performed in clean (particle-free) flames

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

Raman scattering
Raman scattered signal is species specific
can be used for
concentration measurements
Used for measurement of major species concentration
Raman spectrum resides at fixed frequency separation from the
laser line, characteristic of the species
Raman-scattered intensity is directly proportional to the species
number density
Temperature measurements can be made from the distribution
of the scattering
Visible wavelength lasers are used, since scattering scales as
fourth power of Raman frequency
No specific wavelength required
Raman scattering is quite weak
Ratio of collected Raman signal to laser energy ~10-14 in flames
Plagued by S/N ratio problems
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Fluorescence
Precise definition of fluorescence requires that emission occur
between electronic energy states of the same multiplicity,
i.e., electronic spin states
Emission between states of different electronic spin is
phosphorescence
Fluorescence is species specific, and can be used to map minor
species (radicals/intermediates
reaction zone)
Usually, we use fluorescence signature down-shifted in
wavelength from the laser line
To avoid interference from Rayleigh and Mie scattering
Spectrally accessible electronic transitions are typically in the UV,
or require incident UV line
Fluorescence signals are much stronger than Raman signals,
and are more practical for measuring minor species

Aerospace Engineering, IIT Madras

Lectures in Optical Flow and Combustion Diagnostics

CARS
Coherent Anti-Stokes Raman Spectroscopy h L
Anti-Stokes Raman involves energy exchange h s h a
from the molecule to the photon h L
s
Occurs only at elevated temperature L
with sufficient excited state population L
CARS is a non-linear Raman process a
s ro-vibrational
3- or 4-colour technique, usually 3-colour states
Pump beam at L and probe beam at s Stokes-shifted from L
CARS spectra more complicated than Raman spectra
Phase-matching is a problem in dispersed flows
CARS signal many orders magnitude stronger than Raman
Coherent beam permits complete collection
Anti-Stokes region is outside fluorescence or elastic scattering
Useful for major species concentration
Aerospace Engineering, IIT Madras
Lectures in Optical Flow and Combustion Diagnostics

Summary
This lecture consolidates the basis of laser emission and
molecular spectroscopy of chemical species in combusting flow
fields against the common background of quantum mechanics
Both inside the laser and in the diagnosed flow field, the
principle involved is transition of either the laser medium or
the flow medium between its different energy states in
interaction with incident energy quanta
Stimulated emission in laser is collimated by the cavity
mirrors; CARS ensures coherent signals; other signals are
scattered; Mie signal is highly directional
Different types of lasers and their characteristics are listed
Elastic and inelastic scattering phenomena are distinguished
Some practical aspects of Mie scattering are highlighted

Aerospace Engineering, IIT Madras