prof. robert p. lucht school of mechanical engineering, purdue university, w. lafayette, in
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Selective, Sensitive Detection of Dipicolinic Acid and Other Molecules (NO, C 6 H 6 , C 2 H 2 ) Using CARS Techniques. Prof. Robert P. Lucht School of Mechanical Engineering, Purdue University, W. Lafayette, IN Institute for Quantum Studies, Texas A&M University, College Station, TX - PowerPoint PPT PresentationTRANSCRIPT
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Purdue University
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Selective, Sensitive Detection of Dipicolinic Acid and Other
Molecules (NO, C6H6, C2H2) Using CARS Techniques
Selective, Sensitive Detection of Dipicolinic Acid and Other
Molecules (NO, C6H6, C2H2) Using CARS Techniques
Prof. Robert P. Lucht
School of Mechanical Engineering, Purdue University, W. Lafayette, IN
Institute for Quantum Studies, Texas A&M University, College Station, TX
2003 TAMU/DARPA/ONR Workshop on Quantum Optics, Jackson Hole, WY, July 7-11, 2003
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AcknowledgmentsAcknowledgments
• Funding Support from DARPA, DOE Office of Basic Energy Sciences, ARO
• Experiments: Sherif Hanna, Waruna Kulatilaka, Jonathan DuBois (Texas A&M MEEN graduate students), Dr. Zane Arp (now at Los Alamos)
• Modeling: Joel Kuehner (Univ. Illinois)
• Prof. Marlan Scully (Physics), Dr. Tomas Opatrny (Physics), Prof. Phil Hemmer (EE)
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Outline of the Presentation Outline of the Presentation
• Introduction and Motivation
• Laser Diagnostics in Combustion: Dual-Pump CARS
• Electronic-Resonance-Enhanced CARS of NO: Experiments and Modeling
• Electronic Resonance CARS of C2H2
• CARS Detection of Solid DPA
• Conclusions and Future Work
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Triple-pump CARS measurements
performed in laminar hydrogen/air
diffusion flame.
Simultaneous acquisition of
single-shot H2/N2 and H2/O2
spectra demonstrated.
CARS Experiments in Flames CARS Experiments in Flames
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Dual-Pump CO2/N2 CARS Performed in Exhaust of JP8-Fueled Combustor at WPAFB
Dual-Pump CO2/N2 CARS Performed in Exhaust of JP8-Fueled Combustor at WPAFB
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Dual-Pump CARS of N2/CO2Dual-Pump CARS of N2/CO2
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Dual-Pump CARS Spectrum of N2/CO2 from Hencken Burner
Dual-Pump CARS Spectrum of N2/CO2 from Hencken Burner
-20
0
20
40
60
80
100
2250 2300 2350 2400
ExptTheoryExpt - Theory
(CARS Intensity)
1/2 (arb. units)
Raman Shift ( cm -1 )
CO2 Mole Fraction:
From Flowrates = 0.123From CARS = 0.139Temperature = 936 K
N2
CO2
CO2
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Anthrax Spore Detection Anthrax Spore Detection
• Weaponized anthrax mailed to Senate offices, National Enquirer offices Fall 2001
• Anthrax difficult to detect in short period of time
• Anthrax spores can remain dangerous for years
• Anthrax diagnosis must be rapid to prevent severe damage or death
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Ultraviolet Resonant Raman SpectraUltraviolet Resonant Raman Spectra
3b: Calcium Dipicolinate2b: Bacillus Cereus1b: Bacillus Megaterium
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Research Roadmap Research Roadmap
“Ordinary” CARS ERE CARS
Benzene CARSLiquid, 992 cm-1
DPA CARS Powder
Polycrystalline 998 cm-1
NO CARSGas Phase
C2H2 CARSGas Phase
DPA, Benzene CARS
DPA in Spores
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Electronic-Resonance-Enhanced Coherent Anti-Stokes Raman
Scattering (ERE CARS)
Electronic-Resonance-Enhanced Coherent Anti-Stokes Raman
Scattering (ERE CARS)
• ERE CARS was explored as a combustion diagnostic technique by Taran, Attal-Tretout and co-workers from the late 1970s to early 1990s
• Technique was complicated both experimentally and theoretically because only two laser frequencies were used, both electronically resonant
• Our ERE CARS approach is a variant on the dual-pump CARS technique, demonstrated on NO in gas cell to gain understanding of the physics
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Druet and TaranProg Quant Elec1979
ER CARS, Pump 1 = Pump 2ER CARS, Pump 1 = Pump 2
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Electronic Resonance CARS of NO Electronic Resonance CARS of NO
Ground Electronic Level
v" = 0v" = 1v" = 2
v' = 0v' = 1v' = 2
Excited Electronic Level
ΔχCARS ∼ (Δ − i Γ)−1
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Electronic Resonance CARS Detection of NO
Electronic Resonance CARS Detection of NO
λ/2
Pol
λ/2PolPol Beam Dumps
EnergyMeter
Solar-BlindPMT
0.5-MeterSpectrometer
λ/2
591 nm
532 nm
Aperture
Filters70% T 226 nm1%T 236 nm
ER CARS226 nm
Q-switched Nd:YAG LaserInjection-Seeded
Q-switchedNd:YAG Laser
DelayGenerator
GatedIntegrator
Computer NarrowbandDye Laser
472 nm 355 nm
Gas CellNO in N2 Buffer Gas
BBO 2ω Crystal
236 nm
NarrowbandDye Laser
591 nm
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ERCARS Beam Geometry ERCARS Beam Geometry
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Stokes Scan, Fixed Pump 2Stokes Scan, Fixed Pump 2
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NO CARS Spectrum: Theory NO CARS Spectrum: Theory
0 100
2 100
4 100
6 100
8 100
1 101
590.7 590.8 590.9 591 591.1 591.2 591.3 591.4 591.5
Theoretical CARS Spectrum: 1% NO in N2
CARS Signal (arb. units)
Stokes Dye Laser Wavelength (nm)
Pressure = 190 TorrNo resonance enhancement
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CARS Detection of NO CARS Detection of NO
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Electronic Resonance CARS Detection of NO
Electronic Resonance CARS Detection of NO
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Electronic Resonance CARS Detection of NO
Electronic Resonance CARS Detection of NO
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Polarization Suppression of Nonresonant Background
Polarization Suppression of Nonresonant Background
532 nm
591 nm
236 nmNonresonantBackground
NO ResonantCARS Signal
Transmission Axis forPolarizer in CARSSignal Channnel
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NO Electronic Resonance CARS with Background Suppression
NO Electronic Resonance CARS with Background Suppression
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Stokes Scan, Comparison of Theory and Experiment
Stokes Scan, Comparison of Theory and Experiment
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Pump 2 Scan, Fixed StokesPump 2 Scan, Fixed Stokes
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UV Pump Scan, Comparison of Theory and Experiment
UV Pump Scan, Comparison of Theory and Experiment
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Energy Level Diagram Energy Level Diagram
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CARS SusceptibilityNear Electronic Resonance
CARS SusceptibilityNear Electronic Resonance
()()()412312434(0)1221211:,,abbabaaddbddadabccabccaaaccbcaNiiχωωωωωωωγμμωωγμμμμρωωωω−=−+−⏐ ↔√√−−↵⏐ ↔+√+−↵hResonanceenhancement
“Normal” Ramancross section
Raman resonance
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Detailed Energy Level DiagramDetailed Energy Level Diagram
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Acetylene ERE CARS Spectrum Acetylene ERE CARS Spectrum
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
1955 1960 1965 1970 1975 1980 1985
5000 ppm C2H
2
P = 66.7 kPa
λ3 = 239.0 nm
λ3 = 240.5 nm
λ3 = 242.0 nm
CARS Signal (arb. units)
Raman Shift (cm-1)
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Theoretical Acetylene CARS Spectrum
Theoretical Acetylene CARS Spectrum
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
1955 1960 1965 1970 1975 1980 1985
80% C2H
2
P = 60 kPa
CARS Signal (arb. units)
Raman Shift (cm-1)
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Acetylene Electronic Spectrum Acetylene Electronic Spectrum
Watson et al., J. Mol.
Spectrosc. 95, 101 (1982)
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DPA, Benzene CARS SystemDPA, Benzene CARS System
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DPA, Benzene CARS SpectraDPA, Benzene CARS Spectra
0
0.04
0.08
0.12
0.16
960 968 976 984 992 1000 1008
DPA CARSPolycrystalline
Benzene CARSLiquid
CARS Signal (arb. units)
Raman Shift (cm-1)
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ConclusionsConclusions
• NO detected by electronic resonance CARS, spectrum observed clearly for 100 ppm NO
• Sensitive, selective detection of minority species demonstrated, good agreement between model and experiment
• ERE CARS of C2H2 demonstrated, significant resonant enhancement observed
• Very strong CARS signal from DPA demonstrated, narrow spectral feature at 998 cm-1 observed
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Research Roadmap Research Roadmap
“Ordinary” CARS ERE CARS
Benzene CARSLiquid, 992 cm-1
DPA CARS Powder
Polycrystalline 998 cm-1
NO CARSGas Phase
C2H2 CARSGas Phase
DPA, Benzene CARS
DPA in Spores
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Future WorkFuture Work
• Experimental measurements of dissolved DPA and/or solid DPA particles and benzene by ERE CARS
• Study two different ERE CARS schemes for DPA: (1, 2 visible, 3 ultraviolet) or (1, 2 ultraviolet, 3 = 1)
• Work towards ERE CARS microscopy, focus UV beam(s) to less than 10 microns
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ERE CARS of DPA ERE CARS of DPA
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ERE CARS of DPA ERE CARS of DPA
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Multi-Pump CARS Measurements in Combustion Systems
Multi-Pump CARS Measurements in Combustion Systems
• Electronic resonance CARS technique demonstrated in this work is a variant of the technique of dual-pump CARS
• Dual-pump CARS developed for simultaneous measurement of two species in flames
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Electronic Resonance Enhancement Factor
Electronic Resonance Enhancement Factor
λ0 = 532 nm
()()()()43434440434300,accbaccbcccacacacaaccbaccbccaccacaiiiμμμμωωγωωγβωωμμμμωωωωγ⏐ ⏐ √√√√−−−−↵↵=≅⏐ ⏐ √√√−−−↵↵
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Electronic Resonance Enhancement Factor – Saturated 3
Electronic Resonance Enhancement Factor – Saturated 3
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Theoretical Acetylene CARS Spectrum
Theoretical Acetylene CARS Spectrum
0.00
5.00
10.00
15.00
1955 1960 1965 1970 1975 1980 1985
5000 ppm C2H
2
P = 60 kPa
CARS Signal (arb. units)
Raman Shift (cm-1)
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Single-Shot Dual-Pump CO2/N2 CARS Spectrum from JP8-
Fueled Combustor
Single-Shot Dual-Pump CO2/N2 CARS Spectrum from JP8-
Fueled Combustor
0
5
10
15
20
25
30
35
40
1320 1330 1340 1350 1360 1370 1380 1390 1400
ExptTheory
(CARS Intensity)
1/2
Raman Shift (cm-1)
T = 1133 Kx
CO2 = 0.062
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Third-order Perturbation TheoryResult for CARS Susceptibility
Third-order Perturbation TheoryResult for CARS Susceptibility
()()()()()()()412312433444(0)122121211221:,,abbabaaddbaddbddadadbdabccabccaaaccacacacabccabccacbcbcbNiiiiiiχωωωωωωωγμμμμωωγωωγμμμμρωωγωωγμμμμωωγω−=−+−⏐ ↔+√√−−++↵⏐ ↔+√√+−−−↵−+−++h()(0)1bbcaiρωγ⏐ √√+↵
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NO Electronic Resonance CARS with Background Suppression
NO Electronic Resonance CARS with Background Suppression
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Third-order CARS SusceptibilityNear Electronic Resonance
Third-order CARS SusceptibilityNear Electronic Resonance
~0
~0
()()()()()()()412312433444(0)122121211221:,,abbabaaddbaddbddadadbdabccabccaaaccacacacabccabccacbcbcbNiiiiiiχωωωωωωωγμμμμωωγωωγμμμμρωωγωωγμμμμωωγω−=−+−⏐ ↔+√√−−++↵⏐ ↔+√√+−−−↵−+−++h()(0)1bbcaiρωγ⏐ √√+↵
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ER CARS, Pump 1 = Pump 2ER CARS, Pump 1 = Pump 2
Doerk et al.Appl Phys B1997
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Pump 2 Scan, Comparison of Theory and Experiment
Pump 2 Scan, Comparison of Theory and Experiment
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NO Electronic SpectroscopyNO Electronic Spectroscopy
J = N + S
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NO Electronic SpectroscopyNO Electronic Spectroscopy
J = N - S