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How can synchrotron-based FTIR spectroscopy contribute to astrophysical and atmospheric data needs?
A.R.W. McKellar National Research Council of Canada, Ottawa
Herschel Space
Telescope
James Webb Space
Telescope
ALMA Atacama
Large Millimeter
Array
SOFIA StratosphericObservatory For Infrared Astronomy
ACE Atmospheric
Chemistry Experiment
ENVISAT
MetOp OCO (non)Orbiting Carbon
Observatory
Terahertz Remote SensingBillions of $ invested worldwide in THz and IR astronomical and atmospheric missions.
In many cases, the required laboratory data are unavailable, insufficient, or unreliable.
Can synchrotron FTIR help to address this problem?
Synchrotron-based IR spectroscopy
• For some IR applications, SR offers no advantage• But for high spatial resolution (condensed-phase
studies), or very high spectral resolution (gas-phase studies) the brightness of SR is ideal
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100 200 3000
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Inte
nsity
(ar
bitr
ary
units
)
Frequency (cm-1)
SR
/TS
Here, SR gives us 5 to 25 times more signal through a 2 mm aperture than a conventional source. This promises up to 600 times faster data acquisition.
Synchrotron-based IR spectroscopy
• The synchrotron is simply providing a bright continuum source (like a very expensive globar)
• High spectral resolution IR is new for synchrotrons – pioneered at MAXLab and LURE
• New user facilities for high-res (gas-phase) IR spectroscopy are now starting up at CLS, SOLEIL, and the Australian and Swiss Synchrotrons
• Synchrotron advantage is presently limited by noise – mechanical vibrations of the beamline mirrors
High resolution synchrotron IR spectroscopy was pioneered by Bengt Nelander at MAXLab in Lund, Sweden These photos are from 2004
FIR Beamline AILES at Synchrotron SOLEIL near Paris
PascalRoy
Olivier Pirali
The Australian SynchrotronMonash University, near Melbourne
Swiss Light SourcePaul Scherrer Institute, Villigen
(between Zurich and Basel)
Singapore Synchrotron Light SourceISMI infrared beamline
Canadian Light SourceSeptember, 2008
January, 2009
CLS ParametersEnergy: 2.9 GeV
Current: 200 mA
Circumference: 171 m
12 straight sections, 5.2 m long
RF: 500 MHz, 2.4 MV, supercon
Injection: 250 MeV LINAC full energy booster ring
Main building: ~ 85 x 85 m
Bruker IFS 125 HR spectrometer: max optical path difference = 9.4 m instrumental resolution ~ 0.0006 cm-1 (18 MHz)
0.3 m gas cellabsorption paths up to 12 m
2 m gas cellabsorption paths up to 80 mcoolable to ~80 K
Synchrotron-based IR spectroscopy
• With continuing improvements, SR now has a significant advantage from 100 ~ 800 cm-1 at CLS
But we are aiming for better performance
• Reduce noise at source: better isolation of offending cooling pumps, heat exchangers, pipe runs, etc.
• Reduce noise at beamline: more isolation, better mounting of beamline mirrors
• Active optics to stabilize the input radiation on the spectrometer aperture
AcroleinCH2CHCHO(propenal)
• fundamental 8-atom species• planar near-prolate asymmetric rotor • interstellar molecule• combustion byproduct
(forest fires)• potent respiratory irritant (cigarette smoke, smog) E
nerg
y / c
m-1
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131181
131182132
121171
ground state
low lying vibrational states of acrolein
17 band of acrolein, CH2CHCHO
Ka = 7 – 6Q-branch
nominal resolution 0.0012 cm-1
Wavenumber / cm-1
611.3 611.4 611.5 611.6 611.7
Abs
orba
nce
0.0
0.2
0.4
0.6
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Synchrotron, 32 scans
Globar, 300 scans
Synchrotron, 414 scans
Wavenumber / cm-1
158.2 158.3 158.4 158.5
simulation
2 m cell, 0.13 Torr
0.3 m cell, 0.8 Torr
0.0007 cm-1
Acrolein 18 central region
Wavenumber / cm-1
158.20 158.22 158.24 158.26 158.28 158.30
Abs
orba
nce
Acrolein2 m cell, 0.13 Torr
Doppler width ~0.00026 cm-1
Pressure broadening ~0.00050 cm-1
Instrumental width ~0.00064 cm-1
0.0007 cm-1
Acrolein 18 central region
With 0.0007 cm-1 line width and reasonable signal-to-noise ratio, positions can be measured to <<0.0001 cm-1 (for unblended lines).
Half of the acrolein lines here are measured to 0.00003 cm-1 (1 MHz !!) or better.
Pyrrole (c-C4H4NH) 16 bandD.W. Tokaryk & J. Van Wijngaarden (2008)
Azetidine (C3H6NH), 16 bandJennifer van Wijngaarden,
University of Manitoba
400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0
512.0 513.0 514.0 515.0 516.0 517.0 518.0 519.0 520.0 521.0 522.0 523.0 512.0 513.0 514.0 515.0 516.0 517.0 518.0 519.0 520.0 521.0 522.0 523.0
516.6 516.8 517.0 517.2 517.4 517.6 517.8 518.0 518.2 518.4 518.6 518.8 519.0 519.2 516.6 516.8 517.0 517.2 517.4 517.6 517.8 518.0 518.2 518.4 518.6 518.8 519.0 519.2
qQ[(2,5)-(0,4)E]qQ[(3,-10)-(1,-9)E]
qR[(2,14)-(0,13)E]
Methanol (CH3OH) - new high torsional assignmentsL.-H. Xu, R.M. Lees, University of New Brunswick
(vt, K)
CDF3 4 / 3+6 band systemA. Predoi-Cross, LethbridgeP. Pracna, PragueA. Ceausu-Velcescu, PerpignanB. Billinghurst, CLS
CH3COD * 200 K * 48 m pathL.H. Coudert, LISA Université Paris 12
Wavenumber / cm-1
74.1 74.2 74.3 74.4 74.5
Abs
orb
ance
0.0
0.5
1.0 acetaldehyde-d1
CH3CODT = 200 K
pressure = 0.3 Torrpath = 48 m
0.0007 cm-1
Wavenumber / cm-1
507.15 507.20 507.25 507.30 507.35
35Cl35ClCS
35Cl37ClCS
Sum
Experiment
Cl2CS (thiophosgene) 40 m path * 0.02 Torr
Wavenumber / cm-1
507.25 507.26 507.27 507.28 507.29 507.30
~ 0.00075 cm-1
Cl2CS 2 band
~1800 transitions fitted with rms deviation of 0.000065 cm-1 (2 MHz)
How can synchrotron-based FTIR spectroscopy contribute to astrophysical and atmospheric data needs?
Compared to conventional IR sources, synchrotrons promise a combination of– Higher spectral resolution– Higher signal-to-noise ratio– Shorter observation time– Better matching to absorbing molecules (e.g. supersonic jet)
But as observation time becomes shorter we become limited by– Time for sample preparation and change
(e.g. in a large cooled gas cell)– Time for data analysis!!
Coherent Synchrotron Radiation
Wavenumber / cm-1
10 12 14 16 18 20 22 24 26
12 14 16 18 20 22 24 26 J"
N2O pure rotational transitions recorded with coherent synchrotron radiation
Coherent Synchrotron Radiationtends to be noisy because of its nonlinear nature and the presence of beam instabilities
Science Goals Complexes & Clusters
Important intermolecular vibrations are located in the far IR. Spectroscopy directly measures intermolecular forces, important for fields like molecular collisions, condensation, solvation, and energy transfer; also provides stringent & unambiguous tests for quantum chemistry calculations. Sampling techniques: cooled long-path cell; future supersonic jet.
THz Laboratory Astrophysics: Ions & Radicals Far IR is now being explored by astronomers with new aircraft-, space-, and ground-based observatories. It’s the natural wavelength region for observing ‘cool’ matter in the universe (e.g. stellar and planetary formation).
modular 1.5 m gas discharge cellfor unstable astrophysical radicals