two-dimensional chirped-pulse fourier transform microwave spectroscopy amanda shirar june 22, 2010...
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Two-Dimensional Chirped-Two-Dimensional Chirped-Pulse Fourier Transform Pulse Fourier Transform Microwave SpectroscopyMicrowave Spectroscopy
Amanda ShirarAmanda ShirarJune 22, 2010June 22, 2010
6565thth OSU International OSU International Symposium on Molecular Symposium on Molecular
SpectroscopySpectroscopy
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Introduction: 2D Introduction: 2D SpectroscopySpectroscopy
Barbet-Massin, E. Barbet-Massin, E. et al.et al. J. Am. Chem. Soc. J. Am. Chem. Soc. 20102010, , 132132, 5556-5557., 5556-5557. Calhoun, T.; Calhoun, T.; et al.et al. J. Phys. Chem. B J. Phys. Chem. B 20092009, , 113113, , 16291-16295.16291-16295.
NMR IR Visible UV X-ray
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Initial LimitationsInitial LimitationsPulse SequencesPulse Sequences - - Problem:Problem:
- t- t11 Resolution Resolution - Multiple Microwave - Multiple Microwave GeneratorsGenerators
- - Solution:Solution: Arbitrary Waveform Arbitrary Waveform GeneratorGenerator
- Pulse Shaping- Pulse Shaping- Sequence Mode- Sequence Mode
2D CP-FTMW Spectroscopy2D CP-FTMW Spectroscopy- Experimental Procedure- Experimental Procedure- Data Processing- Data Processing
Vogelsanger, Vogelsanger, et atl.et atl. Chem. Phys. Lett.. Chem. Phys. Lett.. 19881988, , 144144, 180-186., 180-186.
1-Chloro-1-Fluoroethylene1-Chloro-1-Fluoroethylene
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CP-FTMW SpectrometerCP-FTMW Spectrometer
13 GHz PDRO
12 GHz Oscilloscop
e (40 Gs/s)
13 GHzFilter
200W
ArbitraryWaveformGenerator
100 MHz Quartz Oscillator
GHz Chirped Pulse0.1-5 GHz
8-18 GHz
Pulsed Nozzle
0.9-10.9 GHz
1)
2)
3)
Free InductiveDecay
18.9 GHz PDRO
10 GHz Bandwidth10 GHz Bandwidth100 ps t100 ps t11 Resolution Resolution
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2D Autocorrelation 2D Autocorrelation SpectrumSpectrum
000000F=1.5F=1.5
111111
Energy Level SchemeEnergy Level SchemeF=1.5F=1.5
F=0.5F=0.5F=2.5F=2.5
1-Chloro-1-Fluoroethylene1-Chloro-1-Fluoroethylene(CFE)(CFE)
Time DomainTime Domain
pu
mp tt11
pro
be
(Scan)(Scan)
11 22 33 44tt
22
A B C
t1 (nsec)
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2D Plots of CFE2D Plots of CFE
000000F=1.5F=1.5
111111
Energy Level SchemeEnergy Level SchemeF=1.5F=1.5
F=0.5F=0.5F=2.5F=2.5
A B C
A
B
C
CFE Assignments CFE Assignments According To:According To:
Leung, H.; Leung, H.; et al.et al. J. Mol. Spec. J. Mol. Spec. 20092009, , 253253, 116-121., 116-121.
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2D Plots of CFE2D Plots of CFE CFE Assignments CFE Assignments According To:According To:
Leung, H.; Leung, H.; et al.et al. J. Mol. Spec. J. Mol. Spec. 20092009, , 253253, 116-121., 116-121.
000000F=1.5F=1.5
111111
Energy Level SchemeEnergy Level SchemeF=1.5F=1.5
F=0.5F=0.5F=2.5F=2.5
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Difficulties of Broadband Difficulties of Broadband 2D2D
ProblemsProblems
Acquisition Time:Acquisition Time:
Resolution in tResolution in t11
Equipment:Equipment:Sampling at Nyquist Sampling at Nyquist
RateRate
Data Storage:Data Storage:Trillion Data pointsTrillion Data points
SolutionSolution
Set Sampling Rate in Set Sampling Rate in tt11
1 ns Step Size:1 ns Step Size:500 MHz Bandwidth500 MHz Bandwidth
0.5 ns Step Size:0.5 ns Step Size:1 GHz Bandwidth1 GHz Bandwidth
1D Slices1D Slices
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Data ProcessingData Processing
Frequency AliasingFrequency Aliasing14.120 GHz 14.120 GHz 120 MHz 120 MHz14.128 GHz 14.128 GHz 128 MHz 128 MHz14.137 GHz 14.137 GHz 137 MHz 137 MHz
A B C
A B
CA
B
C
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Data ProcessingData Processing
PredictedExperimental
Use the Density Use the Density Matrix to predict Matrix to predict
the 1D slicesthe 1D slicesTC09: David TC09: David
WilcoxWilcox
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Further ResearchFurther Research
Kelly Hotopp TC12Kelly Hotopp TC12: Applications of 2D : Applications of 2D CP-FTMW Spectroscopy CP-FTMW Spectroscopy
Non-Selective ExcitationNon-Selective Excitation
Coherence TransferCoherence Transfer
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AcknowledgementsAcknowledgements
• Kelly HotoppKelly Hotopp• David WilcoxDavid Wilcox• Brian DianBrian Dian
• Dr. Henry & Dr. Henry & Camille Dreyfus Camille Dreyfus Foundation - Foundation - Young Faculty Young Faculty ScholarScholar
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BlankBlank
2-D Time Resolved Techniques2-D Time Resolved Techniques - Selective Excitation- Selective Excitation
- Pump single conformation- Pump single conformation - Probe all-conformations- Probe all-conformations
- Relatively simple interpretation - Relatively simple interpretation of of time domain spectrum time domain spectrum
- Non-Selective Excitation- Non-Selective Excitation- Pump all conformers- Pump all conformers- Probe all conformers- Probe all conformers
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AliasingAliasing
Ultra-Broadband scan Ultra-Broadband scan ~~ 2 months 2 months
500 MHz (2048 steps) 500 MHz (2048 steps) ~~ 3.5 hours 3.5 hours
1 GHz (4096 steps) 1 GHz (4096 steps) ~~ 7 hours 7 hours
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Introduction: 2D NMRIntroduction: 2D NMR
-2--2-MicroglobulinMicroglobulin
Benn & Günther, Benn & Günther, Ang. Chem. Int. Ed. Engl. Ang. Chem. Int. Ed. Engl. 19831983, , 2222, 5350-380., 5350-380.
Toluene Toluene DerivativesDerivatives
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Introduction: Further 2DIntroduction: Further 2D
Shim & Zanni, Shim & Zanni, Chem. Phys. Phys. Chem. Chem. Phys. Phys. Chem. 20092009, , 1111, 748-761., 748-761.
Light HarvestingLight HarvestingComplex IIComplex II
Amyloid FiberAmyloid FiberFormationFormation
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2D Rotational 2D Rotational SpectroscopySpectroscopy
J=2J=2
J=1J=1
J=3J=3
Frequency DomainFrequency Domain
MW Pump MW Pump (Single Trans.)(Single Trans.)
MW Probe MW Probe (Broadband)(Broadband)
Benn & Günther, Benn & Günther, Ang. Chem. Int. Ed. Engl.. Ang. Chem. Int. Ed. Engl.. 19831983, , 2222, 5350-380., 5350-380.