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Augustana, March 2, 2007Darin J. Ulness, Concordia College 1Noisy Light Spectroscopy
Noisy LightSpectroscopy:
Putting noise to good use
Darin J. UlnessDepartment of Chemistry
Concordia CollegeMoorhead, MN
TheA
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 2Noisy Light Spectroscopy
OutlineI. IntroductionII. Experiment
• Coherent Raman Scattering
III. Hydrogen Bonding• Pyridine systems
IV. Prospectus
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 3Noisy Light Spectroscopy
SpectroscopyUsing light to gain information about matter
•Transition frequencies•Lineshapes•Susceptibilities
Information Uses of information•In Chemistry•In Biology•In Engineering
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 4Noisy Light Spectroscopy
Light
frequency
Spectrum
time
One frequency (or color)
Electromagnetic radiation•Focus on electric field part
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 5Noisy Light Spectroscopy
Noisy Light: Definition•Broadband•Phase incoherent•Quasi continuous wave
Ele
tric
Fie
ld S
tren
gth
Time
Noi
sy L
ight
Spe
ctru
m
Frequency
Time resolution onthe order of the correlation time, c
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 6Noisy Light Spectroscopy
Experiment•Coherent Raman Scattering: e.g., CARS•Frequency resolved signals•Spectrograms•Molecular liquids
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 7Noisy Light Spectroscopy
Nonlinear Optics
P= ESignal
Material
Light field
Perturbation series approximation
P(t) = P(1) + P(2) + P(3) …
P(1) = (1)E, P(2) = (2)EE, P(3) = (3)EEE
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 8Noisy Light Spectroscopy
CARSCoherent Anti-Stokes Raman Scattering
R
1
12
CARS
1-2= R
CARS= 1 +R
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 9Noisy Light Spectroscopy
CARS with Noisy Light•I(2)CARS
•We need twin noisy beams B and B’.•We also need a narrowband beam, M.•The frequency of B (B’) and M differ by roughly the Raman frequency of the sample.•The I(2)CARS signal has a frequency that is anti-Stokes shifted from that of the noisy beams.
B
B’M
I(2)CARS
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 10Noisy Light Spectroscopy
I(2)CARS: Experiment
Monochromator
NarrowbandSource
BroadbandSource(noisy light)
Lens
Sample
Interferometer
B
B’
MI(2)CARS
ComputerCCD
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 11Noisy Light Spectroscopy
I(2)CARS: SpectrogramMonochromator
NarrowbandSource
BroadbandSource
Lens
Sample
Interferometer
B
B’
MI(2)CARS
ComputerCCD
•Signal is dispersed onto the CCD
•Entire Spectrum is taken at each delay
•2D data set: the Spectrogram
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 12Noisy Light Spectroscopy
I(2)CARS: Spectrogram
Pixel A
A
Pixel B
B
Pixel C
C
Dark regions: high intensityLight regions: low intensity
Oscillations: downconversion of Raman frequency.Decay: Lineshape function
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 13Noisy Light Spectroscopy
SpectrogramNo new information can be extracted.
However…
•Huge oversampling gives much enhanced precision.•Visually appealing presentation of data gives much insight.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 14Noisy Light Spectroscopy
I(2)CARS: Data Processing
18000 18100 18200 18300 18400
-2
-1
0
1
2
BenzeneT22
0 200 400 600 800 1000 1200
0
25
50
75
100
125
150
BenzeneT22
100 200 300 400
0.2
0.4
0.6
0.8
Fourier
Transformation
X-Marginal
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 15Noisy Light Spectroscopy
Virtues of I(2)CARS•Less expensive.•Easier experiment to perform.•Signals are more robust.•Immune to dispersion effects. •Exquisitely sensitive to relative changes in the vibrational frequency and dephasing rate constant.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 16Noisy Light Spectroscopy
Hydrogen Bonding•Interaction between a hydrogen atom and oxygen or nitrogen (or fluorine)
•A very weak chemical interaction (bond)
•A very strong physical interaction
•Exploited extensively in biological systems
O, NO, N
O, NO, N
H
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 17Noisy Light Spectroscopy
Pyridine Systems
Why Pyridine
•Simple molecule
•Important component in many compounds
•Biological importance
•Strong I(2)CARS signal
•H-bond acceptor but not a H-bond donor.
N
C
C
C
C
C
H H
H
H
H
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 18Noisy Light Spectroscopy
Pyridine: Normal Modes
1 990
A1
Ring B
reathing
12 1030
A1
Triangle
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 19Noisy Light Spectroscopy
Pyridine and H-bondingNeat Pyridine•Two peaks
With H-bond•Three peaks
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 20Noisy Light Spectroscopy
Pyridine and H-bondingKey Results
•Some pyridine is free some is hydrogen bonded
•Hydrogen bonding blue-shifts the ring breathing mode
•Hydrogen bonding does not shift the triangle mode
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 21Noisy Light Spectroscopy
Pyridine: Inner Tube Model•Molecular orbitals•Electrostatics•Compare with benzene
•Stabilization through delocalization
•H-bonding makes pyridine more “benzene-like”
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 22Noisy Light Spectroscopy
Pyridine: Inner Tube Model
Electron density for Benzene
= +Electron density for free pyridine
Electron density for H-bonded pyridine
= +
Full e- density e- density sp2 e- density
Full e- density e- density sp2 e- density
≈
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 23Noisy Light Spectroscopy
Pyridine: Test of ModelVary the strength of hydrogen bonding
Formamide N-H-N bond~ 3-4 Kcal/mol
WaterN-H-O bond~ 6-7 Kcal/mol
Acetic AcidProton transfer (acid/base)
980 990 1000 1010 1020 1030 10400.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
Nor
mal
ized
X m
argi
nal i
nten
sity
Raman wavenumber / cm -1
Formamide
Water
Acetic Acid
4 cm-1
8 cm-1
14 cm-1
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 24Noisy Light Spectroscopy
Pyridine: Peak Broadening
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 25Noisy Light Spectroscopy
Peak Broadening ModelsNetwork model
Thermalized distribution model
Etc.
Fileti, E.E.; Countinho, K.; Malaspina, T.; Canuto, S. Phys. Rev. E. 2003, 67, 061504.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 26Noisy Light Spectroscopy
Pyridine/water Temperature
980 990 1000 1010 1020 1030 1040
0.0
0.3
0.6
0.9
1.2
1.5
1.8
2.1
2.4
2.7
3.0
T = -40 O
C
T = -20 O
C
T = 0 O
C
T = 20 O
C
T = 40 O
C
T = 60 O
C
Nor
mal
ized
X m
argi
nal i
nten
sity
Raman wavenumber / cm-1
Xpy = 0.55
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 27Noisy Light Spectroscopy
Pyridine/water TemperatureXpy = 0.55
-40 -20 0 20 40 60
1.0
1.5
2.0
2.5
3.0
3.5
Pea
k w
idth
(ob
s) /
cm
-1
Temperature / O
C
Hydrogen Bonded Ring Breathing Mode
“Free” Pyridine Ring Breathing Mode
Triangle Mode
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 28Noisy Light Spectroscopy
Pyridine/water TemperatureXpy = 0.55
-1
-40 -20 0 20 40 60
988
990
992
994
996
998
1029.5
1030.0
1030.5
1031.0
1031.5
Ram
an W
aven
umbe
r /
cm
Temperature / O
C
Hydrogen Bonded Ring Breathing Mode
“Free” Pyridine Ring Breathing Mode
Triangle Mode
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 29Noisy Light Spectroscopy
ProspectusSummary:•Noisy light provides an alternative method for probing ultrafast dynamics of the condensed phase.•Useful tool for probing hydrogen bonding using “test” molecules.•Simple model useful in understanding hydrogen bonding in pyridine.•Thermalized distribution is likely cause of peak broadening.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 30Noisy Light Spectroscopy
ProspectusFuture of noisy light at Concordia:•Other pyridine based molecules
•Hydroxymethyl pyridine.•Halo pyridines.
•Other nitrogen heterocycles.•A principle goal is to develop an I(2)CARS based microscopy.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 31Noisy Light Spectroscopy
AcknowledgementsFormer StudentsJahan Dawlaty: Cornell University, Ph.D. candidate in optical electronics Dan Biebighauser: Vanderbilt University, Ph.D. in mathematicsJohn Gregiore: Cornell University, Ph.D. candidate in physicsDuffy Turner: MIT, Ph.D. candidate in physical chemistryPye Phyo Aung: John’s Hopkins University, Ph.D. candidate in mathematicsTanner Schulz: University of Minnesota, Ph.D. candidate in physicsLindsay Weisel: Michigan State University, Ph.D. candidate in physical chemistry
Current StudentsBritt BergerZach JohnsonErik BergDanny GreenSarah Freeman
Other Group MembersDr. Mark Gealy, Department of PhysicsDr. Eric Booth, Post-doctoral researcher
FundingNSF CAREER Grant CHE-0341087Henry Dreyfus Teacher/Scholar programConcordia Chemistry Research Fund
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Augustana, March 2, 2007Darin J. Ulness, Concordia College Noisy Light Spectroscopy
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 23Noisy Light Spectroscopy
Pyridine and Water
960 970 980 990 1000 1010 1020 1030 1040
0.0
0.2
0.4
0.6
0.8
1.0 Pyridine/water solution: X(py)=0.6
T = -4o
T = 3o
T = 23o
T = 32o
T = 42o
T = 52o
T = 62o
T = 72o
T = 76o
No
rma
lize
d X
-ma
rgin
al
Wavenumber / cm-1
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 7Noisy Light Spectroscopy
Noisy Light: Alternative•Its cw nature allows precise measurement of transition frequencies.•Its ultrashort noise correlation time offers femtosecond scale time resolution.•It offers a different way to study the lineshaping function.•It is particularly useful for coherent Raman scattering.•Other spectroscopies: photon echo, OKE, FROG, polarization beats…
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 8Noisy Light Spectroscopy
Theory
Optical coherence theory
Perturbation theory: Density operator
Noisy Light Spectroscopy
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 9Noisy Light Spectroscopy
Theoretical Challenges•Complicated Mathematics•Complicated Physical Interpretation
Difficulty•The cw nature requires all field action permutations. The light is always on.•The proper treatment of the noise cross-correlates chromophores.
Solution•Factorized time correlation (FTC) diagram analysis
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 10Noisy Light Spectroscopy
FTC Diagram Analysis
Set of intensity level terms
(pre-evaluated)
Set of evaluated intensity level
terms
Messy integration and algebra
Set of FTC diagrams
ConstructionRules
EvaluationRules
Physicshard hard
easy
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A1Noisy Light Spectroscopy
Utility of FTC Diagrams•Organize lengthy calculations•Error checking•Identification of important terms•Immediate information of about features of spectrograms•Much physical insight that transcends the choice of mathematical model.
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A2Noisy Light Spectroscopy
Example: I(2)CARS
P(t,{ti})
P(s,{si})
arrow segments: B, B’ correlation
-dependentline segments: B, B or B’,B’ correlation
-independent
FTC analysis•Each diagram with arrows has a topologically equivalent partner diagram containing only lines: 2:1 dynamic range•Each diagram with arrows has a topologically equivalent partner diagram that has arrows pointing in the opposite direction: signal must be symmetric in
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 4Noisy Light Spectroscopy
Modern SpectroscopyFrequency Domain•Measure Spectra•Examples
•IR, UV-VIS, Raman•Material response
•Spectrally narrow•Temporally slow
Time Domain•Response to light pulse•Examples
•PE, transient abs.•Material response
•Spectrally broad•Temporally fast
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 4Noisy Light Spectroscopy
Modern SpectroscopyFrequency Domain•Measure Spectra•Examples
•IR, UV-VIS, Raman•Material response
•Spectrally narrow•Temporally slow
Time Domain•Response to light pulse•Examples
•PE, transient abs.•Material response
•Spectrally broad•Temporally fast
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Augustana, March 2, 2007Darin J. Ulness, Concordia College 4Noisy Light Spectroscopy
Modern SpectroscopyFrequency Domain•Measure Spectra•Examples
•IR, UV-VIS, Raman•Material response
•Spectrally narrow•Temporally slow
Time Domain•Response to light pulse•Examples
•PE, transient abs.•Material response
•Spectrally broad•Temporally fast
Is there another useful technique?Noisy light? YES!
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A3Noisy Light Spectroscopy
Example: I(2)CARS
Pixel A
A
Pixel B
B
Pixel C
C
The I(2)CARS data shows • 2:1 dynamics range• symmetry
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A4Noisy Light Spectroscopy
0 1 2 3 4 50.00
0.05
0.10
0.15
0.20
0.25
0.30
s
S/N
(a)
0 1 2 3 4 50.00
0.05
0.10
0.15
0.20
0.25
0s
D
S/N
(b)
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A5Noisy Light Spectroscopy
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A6Noisy Light Spectroscopy
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A7Noisy Light Spectroscopy
-20 0 20 40 60 800.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
Fit Results:ratio =0.00783 T + 0.905R = 0.9942
Fre
e p
yr.
to
H-b
ou
nd
pyr
Temperature (Co)
- ∆G° Product Favored
- ∆H° Exothermic
- ∆S° Entropically unfavorable
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Augustana, March 2, 2007Darin J. Ulness, Concordia College A8Noisy Light Spectroscopy
17300 17400 17500 17600
-400
-200
0
200
400
pyridine with .4g AgNO3
960 970 980 990 1000 1010 1020 1030 1040-0.2
0.0
0.2
0.4
0.6
0.8
1.0Pyridine / AgNO
3
g AgNO3/ml py 0.00 0.061 0.097 0.121 0.170 0.238 0.298 0.341 0.409
No
rma
lize
d X
-ma
rgin
al
Wavenumber / cm-1
0.00 0.05 0.10 0.15 0.20 0.25-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4 Pyridine/AgNO3
Ratio
27.1 Xeff
2 -.97 X
eff + 0.013
Co
mp
lexe
d p
yri
din
e t
o
Fre
e p
yri
din
ed
Effective mole fraction AgNO3
complex = Icomplex
free xfree
Icomplex = Ifree at 0.21 mole fraction
complex = 1
free .79
complex = 3.76
free