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CHEIRON SCHOOL OCT 5, 2008 1
Far-IR/THz & High Spectral Resolution Spectroscopy Using Synchrotron Radiation
Dominique AppadooSenior IR Beamline Scientist
CHEIRON SCHOOL OCT 5, 2008 2
Melbourne
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Number of beamlines
Purpose Status
North America ALS Berkley 1 Microscopy and Far-IR Operational CAMD Baton Rouge 1 Microscopy Planned CLS Saskatoon 2 1 Microscopy, 1 Far-IR Operational NSLS Brookhaven 6 3 Microscopy, 2 Far-IR, 1 THz Operational Surf III Gaithersburg 1 Microscopy Planned SRC Madison 1 Microscopy Operational Asia and Australia Australian Synchrotron
1 Microscopy and Far-IR Operational
INDUS I, India 1 Microscopy Planned Helios II, Singapore 1 Microscopy and Far-IR Operational NSRRC, Taiwan 1 Microscopy Operational NSRL, Heife 1 Microscopy and Far-IR Planned BSRF, Beijing 1 Microscopy Planned Spring-8, Himeji 1 Microscopy and Far-IR Operational UVSOR, Okazaki 1 Far-IR Operational Europe ESRF, Grenoble 1 Microscopy Operational Soleil, St. Aubin 2 1 Microscopy, 1 Far-IR Commissioning ELETTRA, Trieste 1 Microscopy and Far-IR Operational DAPHNE, Frascati 1 Far-IR Operational SLS, Villigen 1 Microscopy and Far-IR Commissioning ANKA, Karlsruhe 1 Microscopy and Far-IR Operational BESSY II, Berlin 1 Microscopy and Far-IR Operational DELTA, Dortmund 1 Microscopy Planned MAX II, Lund 2 Microscopy and Far-IR operational DIAMOND, Didcot 1 Microscopy Planned
Infrared beamlines worldwide
32 IR Beamlines
CHEIRON SCHOOL OCT 5, 2008 4
Far-IR/THz ≡ XSX→ eXtremely Soft X-ray
= 1000 – 10 μm= 10 – 1000 cm-1
= 0.3 – 30 THz= 1 – 124 mEV
λννE
The far-IR/THz spectral region
wwww.lbl.gov/MicroWorlds/ALSTool/EMSpec/EMSpec2.html
THz Energy Gap
PhotonicsElectronics
- lack of adequate tunable lasers- weakness of conventional thermal sources- difficulties with far-IR detectors
CHEIRON SCHOOL OCT 5, 2008 5
The Final Frontier
- cw & pulsed THz lasers are now available- Backward-wave oscillators- Accelerator-based sources …
CHEIRON SCHOOL OCT 5, 2008 6
What kind of interactions take place in the far-IR?
• rotation of smaller molecules• ro-vibration of larger molecules- surface/adsorbate interactions
- biological processes- chemical dynamics
van der Waals energies
phonon modes
H-bonding
P R v = 0
v = 1
v = 2
Rotational manifolds
Q
CHEIRON SCHOOL OCT 5, 2008 7
– How does energy flow within a molecule?– What is the nature of the weak attractive forces that exist
among atoms and molecules?– How do metal atoms bond to other chemical groups?– What are the structures of long carbon chain molecules?– How do the optical properties of a material change under ultra-
high pressures?
What can we learn from these interactions?
... this is just the beginning!
CHEIRON SCHOOL OCT 5, 2008 8
I. IR Spectroscopy
II. Synchrotron IR Radiation
III. The IR Beamline at the Australian Synchrotron
IV. FT Spectroscopy
V. Applications of Far-IR & High Resolution Synchrotron Spectroscopy
VI. Coherent Synchrotron Radiation
Overview
CHEIRON SCHOOL OCT 5, 2008 9
I. Introduction to IR spectroscopy
CHEIRON SCHOOL OCT 5, 2008 10
http://www.brukeroptics.com/downloads.html
Fingerprint spectral region
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IR spectroscopy of condensed samples:Vibrational Spectroscopy → spatial resolution
Abs
orba
nce
PO32- stretching
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1)
Amide IC=O
Amide IIC-N and N-H
CH2 and CH3stretching
CH3 bending
Broad O-H and N-HStretching
PO2- stretching
C-O stretch
CO2
ν-shiftsrelative intensities
Spatial resolution required
CHEIRON SCHOOL OCT 5, 2008 12
Diatomic molecules
Polyatomic molecules: linear 3N-5 modes non-linear 3N-6 modes
IR spectroscopy of gas-phase samples:Ro-Vibrational Spectroscopy → Spectral Resolution
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V = 1
Potential energy curve of a diatomic molecule in itsground electronic state.
re
De
ωe
Manifold of rotational stateswithin each vibrational level
P Rv = 0
v = 1
v = 2
Rotational manifolds
QJ=0
J=5
CHEIRON SCHOOL OCT 5, 2008 14
Diatomic ModelE(v,J) = Te + G(v) + Fv(J)
Be α 1/μre2
whereBv = Be – αe(v+ ½ ) + βe(v+ ½ )2 + …
ωe is the fundamental frequency (α μ-1/2)re is the bond lengthDe is the dissociation energy
where G(v) = ωe(v+ ½ ) – ωexe(v+ ½ )2 + ωeye (v+ ½ )3 + …Fv(J) = Bv J(J+1) – Dv (J(J+1))2 + Hv (J(J+1))3 + …
De ~ Σ ΔGvV=0
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Absorption Spectroscopy…
I1I0
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Rotational, vibrational and electronic Transitions
P Rv = 0
v = 1
v = 2
QJ=0
J=5
ΔErot ΔEvib ΔEelec
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IR emission spectrum of ZnD (2Σ)
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Life can get complicated even for diatomics
IR spectrum of MnH (7Σ)Δν= 0.006 cm-1
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1122.66391122.6580
Δν~0.006 cm-1
IR spectrum of MnH (7Σ)
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Simply put, spectra for diatomic molecules can be complicated and congested!
- Heavy molecules: closely-spaced transitions, overlapping bands, and narrow linewidths
- Presence of naturally occurring isotopomers in measurable quantities
- High-spin electronic states due to open-shells: spin-splitting
… Need high spectral resolution!
CHEIRON SCHOOL OCT 5, 2008 21
Normal modes of vibration of R152a3N-6 modes where N=8 ≡ 18 modes
C
HF
C
F
H
HH
Polyatomics:Asymmetric Top Molecule
10 001 1001200130 0140 015 00
W a v e n um be r cm -1
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Abs
orba
nce
Uni
ts
IR Spectrum of R152a at low resolution
ν4
ν5
ν6
ν8
ν16
C-C
CH3 def.
CF2
CH3 rock
ν7
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100011001200130014001500
Wavenumber cm-1
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Abs
orba
nce
Uni
ts
Part of the IR spectrum of R152a
ν4
ν5
ν14 ν6
ν9+ν17 ?
ν7 ν15 ν16
ν8
Low resolution EFC spectrum
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<v:J,K|H| v:J,K> = v + J(J+1) + ( A - ) K2
- ΔJJ [J(J+1)]2 - ΔJK J(J+1) K2 - ΔKK K4
+ ΦJJJ [J(J+1)]3 + ΦJJK [J(J+1)]2 K2 + ΦJKK [J(J+1)] K4 + ΦKKK K6
- ΛJJJJ [J(J+1)]4 - ΛJJJK [J(J+1)]3 K2 - ΛJJKK [J(J+1)]2 K4 - ΛJKKK J(J+1) K6 -ΛKKKK K8 ….
<v:J,K|H| v:J,K ± 2> = [ ½ - δJJ(J+1) - δK{(K ± 2)2 + K2}
+ φJJ [J(J+1)]2 + 1/2φJK [J(J+1)] {(K ± 2)2 + K2} + 1/2φKK {(K ± 2)4 + K4}
- λJJJ [J(J+1)]3 - λJJK [J(J+1)]2 {(K ± 2)2 + K2} - λJKK [J(J+1)] {(K ± 2)4 + K4}
- λKKK {(K ± 2)6 + K6} … ] F± (J,K) F± (J,K ± 1)
where F ±(J,K) = { J(J+1) - K(K ± 1) }1/2
= 1/2 (B-C)
B_
B_
B_
B_
Asymmetric Rotor Model
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Pyrrole at 0.00096 cm-1 (~0.1 μeV)
wavenumbers / cm-1
Δ = 0.01 cm-1
δ = 0.00107 cm-1
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Spectroscopic issues to contend with
• Overlapping & Hot bands• Coupling of vibrational modes: Coriolis and Fermi resonnances• Closely spaced lines & Narrow linewidths as the MW increases• Isotope splitting• Hyperfine structure
.... Clearly we need high spectral resolution in order to resolve these narrow spectral lines!
How high a resolution is required?
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Observed Linewidth:
Different factors contribute to the width of an observed transition
ΔνObs ~ √ ΔνDop2 + Δνcol
2 + ΔνILW2
Therefore, the observed linewidth can be minimised by reducing the Temperature and Pressure!
Instrument linewidth ≡ ΔνILW dictated by apodisation function
Doppler width, ΔνD = 2ν √ 2ln2k/c2 √ T/M ~ 7.16E-7 ν √ Τ/Μ
Pressure broadening, Δνcol = 16pr2/√πMkT ~ 3Ε-4 cm-1 / Torr
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Spectroscopic issues to contend with
• Small quantity of sample to minimize Pressure broadening effects or hard to synthesize
• Isotopologues with low natural abundance• Weak absorbers
.... Need bright source!
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II. SYNCHROTRON INFRARED LIGHT
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Infrared mission from a synchrotron bending magnet
Edge Radiation and Bending Magnet Radiation
• Bright• Broadband• Pulsed• Polarized
Large vertical divergenceRelative to X-ray beam
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Port 02B1-1 @ CLS: Far-IR
55×37 mrad2
~ 40 cmē beam
ΘH = 55 mrad
ΘV = 37 mrad
SV = 13 μm
SH = 480 μm 2.0
1.5
1.0
0.5
0.0
Power density (x10-3
W/mm2)
-6-4
-20
24
6
Mirror length (m
m)
SV
SH
ΘH
ΘvX-Rays
λ
λ
IR
IR
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Is the synchrotron IR beam very intense?
1 E16
1 E15
1 E14
Flux ( in Photons/s/0.1%
bw)
Far- IRMid- IR
I=800 mA
0.8 GeV, 90x90 mrad, 800 mA
1 10 100 1000 100001E-11
1E-10
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1SOLEIL 20x78 mrad I= 500 mABlackBody 2000°K
Wat
ts/c
m-1
/mm
2 sr
Wavenumbers / cm-1
It’s the synchrotron brightness that counts
CHEIRON SCHOOL OCT 5, 2008 32
SR Advantages over thermal sources
• Brightness: better S/N• Small source: better throughput with small
samples• Highly collimated: higher resolution achievable• Polarized: ellispsometry • Pulsed: pump & probe experiments
CHEIRON SCHOOL OCT 5, 2008 33
Far-IR SR wavelength limits• Height of dipole chamber:
λo = 2h√h/Rwhere h is the height of the dipole chamber and R the radius of the bend magnet
• Extraction aperture:λc = R(ΘNat/1.66188)3
where ΘNat represents the vertical angle in radians
CHEIRON SCHOOL OCT 5, 2008 34
EXTRACTION OF SYNCHROTRON IR RADIATION
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Optical Layout at the CLSM2
DW
M1
M3
M4
M5
M6
M7
M8Ge:Cu
2. Mirror M1 inserted into dipole “crotch” from above or below
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2. Mirror M1 inserted into dipole “crotch” from above or below
e.g. Soleil, ESRF…
M1 Mirror with thermocouple wires
Top view of mirror insertion portImages courtesy of Paul Dumas, Soleil.
Dipole Multipole
M1
M2
CHEIRON SCHOOL OCT 5, 2008 37
-14 mrad +44 mradZero degree line
Mirrorinsertion port Beam extraction port
3. Mirror inserted into dipole chamber from side
e.g. Australian Synchrotron
Which brings us to…
CHEIRON SCHOOL OCT 5, 2008 38
III. The Australian SYNCHROTRON INFRARED BEAMLINE
CHEIRON SCHOOL OCT 5, 2008 39
Mirror in
IR beam out
Electron beam
Adapted Infrared Dipole Chamber at Australian Synchrotron
CHEIRON SCHOOL OCT 5, 2008 40
Beamsplitteroptics Diamond Window and
Gate Valves
M1 mirrormechanism
Matching optics forHigh Resolution FTIR
Focusing andSteering mirrors
Matching optics forIR Microscope
Infrared beamline showing (from right) synchrotron beam entering front end optics (M1, M2, M3, M3a), diamond exit window, beamsplitter optics vessel and matching optics boxes for
the two endstation instruments.
Storage ring wall
CHEIRON SCHOOL OCT 5, 2008 41
SR beamsplitter vacuum chamber
Microscope beamline Far-IR & High-Res Beamline
CHEIRON SCHOOL OCT 5, 2008 42
Visible light in the beamsplitter vessel at theAustralian Synchrotron Infrared beamline
Edge & Bend Magnet radiation to “THz & high resolution” spectrometer
Bending magnetradiation to “microscope”
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Horizontal position / mm-40 -20 0 20 40
Vert
ical
pos
ition
/ m
m λ = 10 µm
604020
0-20-40-60Ve
rtic
al p
ositi
on /
mm λ = 100 µm
-80 -60 -40 -20 0 20 40 60 80
Edge Radiation
Edge Radiation
Bending Magnet Radiation
Bending Magnet Radiation
30
20
10
0
-10
-20
-30
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IR beam profile – comparison with SRW
CHEIRON SCHOOL OCT 5, 2008 45
INFRARED BEAMLINE INSTRUMENTATION
CHEIRON SCHOOL OCT 5, 2008 46
Infrared Beamline at the Australian SynchrotronMicroscope Branch
Bruker V80v with Hyperion 3000 microscope
250×250 μm2 Wide- Band MCTOption for bolometer
50×50 μm2 Narrow-Band MCT
Confocal point scanning - current technology
TransmissionTrans-ReflectionGrazing Incidence AngleAttenuated Total Reflectance
CHEIRON SCHOOL OCT 5, 2008 47
Focal Plane Array - next technology
64x64 photovoltaic MCT Focal Plane Array
Microscope Branch
CHEIRON SCHOOL OCT 5, 2008 48
Infrared Beamline at the Australian SynchrotronHigh Resolution branch
Bruker IFS 125HR FTIR Spectrometer
Beamsplitters
IR Detectors
• Multi/Mylar• Ge/KBr
• Si bolometer• Si:B bolometer• DTGS• MCTN• MCTM
Sources• Synchrotron• Hg-Arc lamp• Globar• Tunsten lamp
Optical Filters• series of narrow band pass IR filters
Apertures• 0.5 – 12.5 mm
10 – 370 cm-1
300 – 1850 cm-1
100 – 3000 cm-1
700 – 5 000 cm-1
600 – 5 000 cm-1
30 – 630 & 12 – 35 cm-1
450 – 4 800 cm-1
mw – vis5 – 1 000 cm-1
10 – 13 000 cm-1
1 000 – 25 000 cm-1
OPD: 942 cm → resolution ≥ 0.00096 cm-1 (0.1 μeV)Optics: f/6.5
Sample compartment: cells ≤ 30×20×10 cm3
CHEIRON SCHOOL OCT 5, 2008 49
Observed Linewidth: ΔνObs ~ √ ΔνDop2 + Δνcol
2 + ΔνILW2
Therefore, the observed linewidth can be minimised by reducing the Pressure and Temperature!
Recall …
CHEIRON SCHOOL OCT 5, 2008 50
50 cm Multipass gas cell for high resolution spectroscopy of room temperature samples
Small quantity of sample to minimize Pressure broadening effects
Recall that Absorbance α εclwhere c is the concentration and l the interaction path.
CHEIRON SCHOOL OCT 5, 2008 51
Enclosive Flow Cooling multipass cell for gas-phase studies at cryogenic temperatures.
MCT detector
CEP
300
495
165colander
vacuuminsulation
evacuationport
N2 gas
sample
flow of cold N2
liq. N2
heated mirror
CHEIRON SCHOOL OCT 5, 2008 52
0.0
0.2
0.4
0.6
0.8
1.0
0.00
0.05
0.10
0.0
0.2
0.4
0.6
0.8
1.0
2250 2220 2190
wavenumber / cm-1
Abs
orba
nce
Uni
tsN2O mid-IR spectrum ( 0.002 cm-1 )
Cluster formation
Trot = 112 K
Trot = 302 K
Trot = 112 K
CHEIRON SCHOOL OCT 5, 2008 53
Supersonic Jet Expansion chamber
More Scientific Apparatus
Diamond Anvil Cell
Metal foil gasket
< 100 μm
Grazing Incidence Angle Cell
CHEIRON SCHOOL OCT 5, 2008 54
IR Cryostat for matrix isolation studies
Minimise H2O interferenceIncrease Absorption coefficient for a range of substances
Down to 10 K!
Low freq. vibrations of biological samples
CHEIRON SCHOOL OCT 5, 2008 55
Assessing beamline performance
CHEIRON SCHOOL OCT 5, 2008 56
Beamline 11 at SRS - unapertured beam profile at sample stage. Area mapped = 30x30 µm. Beam halfwidth = 8x8 µm.
Synchrotron infrared beam focused on sample
Performance of the microscope beamline
CHEIRON SCHOOL OCT 5, 2008 57
Absorbance spectra of tissue sample recorded at 10µm spatial resolution under identical collectionconditions using a Globar™ infrared source andsynchrotron radiation.
Advantage of using a synchrotron seen in spectra…
CH stretch absorption bands from 5micron spot in tissue sample.Equivalent spectra recorded usingsynchrotron (top) and Globar(bottom).
3100 3000 2900 2800
Wavenumbers / cm-1
CHEIRON SCHOOL OCT 5, 2008 58
Testing the IR Beamline Performance withCustom Resolution targets
CHEIRON SCHOOL OCT 5, 2008 59
WAVELENGTH DEPENDENCE OF MICROSCOPE SPATIAL RESOLUTION DEMONSTRATED AT INFRARED BEAMLINE
Polymer pattern on CaF2produced by
photolithographyIR absorbance image
At 2935 ±125 cm-1
CH band region
IR absorbance imageAt 1701 ±59 cm-1
C=O band region
20µm
CHEIRON SCHOOL OCT 5, 2008 60
5
10
20
30
40
Rat
io o
f Int
ensi
ties
SR / Hg
SR
Hg
100 200 300
100 × SR10
20
15
100 × GB
600 700
SR /GB
5
500
GB
SR
1
2
3
4
SR /GB
800 900 1000
IIIIII
Energy / cm-11000200 400 600 800
1
2
3
4
10-1
3×
Phot
ons/
s/0.
1%B
W
1475 K Blackbody
SR 200mA, (57×35) mrad2
~18 ×
~4 ×
~7.2 ×
2.0 mm 1.3 mm 1.15mm
~8 ×
~4.4 × ~5 ×
Ge:Cu / KBr MCTn / KBrBolometer / 6μm Mylar
Performance of the far-IR beamline
CHEIRON SCHOOL OCT 5, 2008 61
Spectrum of Pyrrole at 0.001 cm-1 resolution
10 hrs
40 daysGLOBAR
SYNCHROTRON
CHEIRON SCHOOL OCT 5, 2008 62
IV. Introduction to Fourier transform Infrared spectroscopy
CHEIRON SCHOOL OCT 5, 2008 63
Interferogram
Frequency components of the interferogram
FT spectrum
scanner distanceA
mpl
itude
Fourier transform spectroscopy
M2
D1
D3 D4
D2
D5 D6
sample
compartment
S4
S1S2S3
AC
AC
FC
M1BS
frontchannel
backchannel
Brüker IFS120HR
S1-S3 Internal SourcesS4 External SourceAC Aperture ChangerFC Filter ChangerBS BeamsplitterM1-M2 RetroreflectorsD1-D6 Detectors
Res = 0.9/OPD
OPD = SCL/2
CHEIRON SCHOOL OCT 5, 2008 64
Many frequencies are present in the infrared beam
Position of “zero path difference”
CHEIRON SCHOOL OCT 5, 2008 65Position of “zero path difference”
Summing of all frequencies for each position of the mirror
CHEIRON SCHOOL OCT 5, 2008 66
-5-4-3-2-101234
Volts
200 400 600 800 1000 Data points
“Centre burst” at Zero Path Difference
1234567891011
Sing
le B
eam
500 1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1)
Interferogram Single Beam SpectrumFourier
Transform
Data output from FTIR system
CHEIRON SCHOOL OCT 5, 2008 67
1234567891011
Sing
le B
eam
500 1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1)
1234567891011
Sing
le B
eam
500 1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1)
Background Single Beam Spectrum
Sample Single Beam Spectrum
0.10
0.20
0.30
0.40
0.50
0.60
Abs
orba
nce
500 1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1)
Sample Absorbance Spectrum
Data output from FTIR system
A
A
B
Log(A/B)
CHEIRON SCHOOL OCT 5, 2008 68
Pros and Cons of Fourier transform spectrometryAdvantages over grating spectrometers• Felgett or Multiplex• Jacquinot or throughput: apertures instead of slits • High wavenumber accuracy: sampling λHeNe/2• High resolving power: ~ 106
• Fast
Disadvantages• Complex system (but can be used as a black box by Users)• Expensive ....• Can take a lot of room!
CHEIRON SCHOOL OCT 5, 2008 69
V. APPLICATIONS OFSYNCHROTRON INFRARED LIGHT
CHEIRON SCHOOL OCT 5, 2008 70
837-1165 cm-1
2790-2989 cm-1
Applications of synchrotron IR radiation with a microscopeATR objective
Cross sections of agricultural soils: analysis of distribution and forms of carbon functional groups
Peter Fisher, Matt Kitching (DPI Victoria) / Simon Lewis, Bill van Bronswijk (Curtin University) Kenneth Paul Kirkbride, Vincent Otieno-Alego (AFP) / Alana Treasure, Dudley Creagh (Uni Canberra)
Forensic examination of paper documents
10 microns aperture, 5 microns steps
Cellulose Ink CaCO3
100 μm
2850 - 3023 cm-1 1580 - 1600 cm-1 856 – 897 cm-1
19th century parchment sample
100 μm
CHEIRON SCHOOL OCT 5, 2008 71
Grazing angle objective
Donna Menzies, Thomas Gengenbach, Celesta Fong, John Forsythe, Ben Muir – CSIRO / Monash
Protein resistant plasma polymer thin films
Plasma polimerisation technique used to produce high throughput gradient PEG (poly (ethylene glycol) based films on a nanometer scale.
Systematically varied chemistry by altering the plasma processing conditions.
Study the mechanism of protein repellant properties of PEG coatings.
Ether/hydrocarbon ratio of DGpp gradient films
2.05
2.1
2.15
2.2
2.25
2.3
2.35
2.4
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2
COC/CH
dist
ance
from
ra
zor
(mm
)
Diethylene glycol dimethyl ether (DG)
COC ether
COCH2
OH
CHEIRON SCHOOL OCT 5, 2008 72
SINGLE CELL WORK
10 × 10 µm aperture
Live Human Mesenchymal Stem Cells
70 μm
10 μm
Fixed mouse Oocyte Cell
Live Leukaemia Cells
Fixed Malaria infected RBCs8 x 8 μm
CHEIRON SCHOOL OCT 5, 2008 73
Response of single living phytoplankton cells to changes in the environment
Phil Heraud, Sally Cane, Anthony Eden, Don McNaughton, Bayden Wood, Monash University
Lipid concentration FTIR maps
Control
Nitrogen starved cell Re-supplied with nitrogen
Freshwater alga Micrasterias hardyi.
CHEIRON SCHOOL OCT 5, 2008 74
- prototype system for torsional motion - Intramolecular Vibl Redistribution- Earth and Jovian atmospheres- Pluto: clues to evolution
early solar system
Ethane
Methyl SilaneSaturn
Titan
Molecular species of Astrophysical interest
Applications of synchrotron IR radiation with a High-Resolution FT spectrometer
CHEIRON SCHOOL OCT 5, 2008 75
Telescope missions in the submillimeter region for the study of star formation
- Herschel Space Observatory (2008, 3-4 years)- Stratospheric Observatory for Infrared Astronomy: SOFIA (2010, 20 years)- Atacama Large Millimeter Array: ALMA (2011, decades)
Astrophysical weed-molecules & their isotopologues
-Class I: CH3OH, HCOOCH3, CH3OCH3, C2H5CN
WAVENUMBER / CM-1
CH3-18OH 13CH3-OH
Molecular species of Astrophysical interest
Recorded at the CLS
CHEIRON SCHOOL OCT 5, 2008 76
Far-IR spectroscopy of aromatic cycles containing heteroatomsDennis Tokaryk (U. of New Brunswick) & Jen van Winjgaarden (U. of Manitoba)
pyrrole furan thiophene
O SHN
These heterocycles and their derivatives are:
• building blocks of organic chemistry-pharmaceuticals, agrochemicals, dyes
• constituents of biologically active moleculesuch as heme and chlorophyll
• byproducts of combustion processes
• candidates for interstellar detection
• solvents/additives in industrial processes• naturally found in wood, petroleum
CHEIRON SCHOOL OCT 5, 2008 77
Strong positive pleochroism at 146 cm-1 – implies out-of-plane mode Slight negative at 167,189, 264 cm-1 – implies in-plane modeNo change at 110 cm-1 – expected if interlayer cation ‘rattle’
50o
35o
20o
10o
0o
Spotted Tiger Muscovite – self supported crystal: Mylar multilayer beamsplitter, Si Bolometer
SR
To better understand the dynamics of cation exchange reactions of important minerals, commonly used as environmental barriers to contaminated wastes such as radionuclides
Samples of Environmental interest
CHEIRON SCHOOL OCT 5, 2008 78
VI. COHERENTSYNCHROTRON RADIATION
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5
10
20
30
40
Rat
io o
f Int
ensi
ties
SR / Hg
SR
Hg
50 100
Energy / cm-1
Apt=2.0 mm
Bolometer / 6μm Mylar
Incoherent Synchrotron < 100 cm-1
CHEIRON SCHOOL OCT 5, 2008 80
Coherent Synchrotron Radiation
BESSYwebsite
PSR α N + N2e-(ω /c)σz2
CHEIRON SCHOOL OCT 5, 2008 81
81
CSR at the CLS
CHEIRON SCHOOL OCT 5, 2008 82
6 8 10 12 14 16 18 20
02
46
810
1214
9 10 11 12 13 14 15 16 17 18J”= 19 20
wavenumber / cm-1
recorded with the Coherent SR at a resolution of 0.025 cm-1
46 scans co-added
Period ~ 0.0731 cm-1
N2O THz absorption spectrum
82
CHEIRON SCHOOL OCT 5, 2008 83
• Synchrotrons provide intense beams at long wavelengths into the Far-IR
• IR spectroscopy is used to provide information on the chemicalcomposition of materials based on the vibration of the bonds present.
• Synchrotron IR allows these measurements to be made rapidly at a few microns dimension (micoscope), or at low concentration(and high SPECTRAL resolution).
• Synchrotron IR has applications in a diverse range of research areas.
• Future developments in the field will allow imaging below the diffraction limit and the use of intense Far-IR and Terahertz beams
Summary
CHEIRON SCHOOL OCT 5, 2008 84
Acknowledgements
• Dudley Creagh – Canberra University• Don McNaughton – Monash Univerrsity• Phil Heraud – Monash Immunology and Stem Cell Laboratories• Bayden Wood – Monash University• Liz Carter – University of Sydney• Peter Lay – University of Sydney• Mark Hackett – University of Sydney• Sally Caine - Monash Immunology and Stem Cell Laboratories• Vivienne Juan - Monash Immunology and Stem Cell Laboratories• Alice Brandli – Monash University• Cassie Jean – Monash University• Alana Treasure – Univerrsity of Canberra• Bill van Bronswijk – Curtin University• Evan Robertson – Monash University• Ljiljana Puskar – Monash University• Tarekegn Chimdi – Monash University• Paul Dumas – Soleil• Mike Martin – ALS• Ulli Schade - BESSY II• David Moss – ANKA• Yves-Laurant Mathis – ANKA• Jonathan McKinlay – Australian Synchrotron• Nati Salvado – University of Barcelona• Azzedine Hammiche – University of Lancaster• John Prag – Manchester Museum• FMB – Berlin• Biolab/Bruker Instruments
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Thanks…Dominique Appadoo
Australian Synchrotron800 Blackburn Road
Clayton 3168 VICAUSTRALIA
Tel: (03) 8540 4127Email: dominique.appadoo@synchrotron.vic.gov.au
CHEIRON SCHOOL OCT 5, 2008 86
Infrared SpectroscopyEnergy range
0.001 eV to 1 eV (10 cm-1 to 10,000 cm-1)Property accessible
molecular vibrations & rotationsMeasurements
vibrational & rotational spectraInformation
molecular structure, chemical analysis
Synchrotron Benefitssignal to noise, spatial resolution(down to the diffraction limit)
AS Contact Scientists
Dr Mark Tobin, 613 8540 4172Dr Dominique Appadoo, +613 8540 4127 Dr Lillijana Puskar, 613 8540 4185