the infrared spectrum of ch 5 + revisited
DESCRIPTION
The Infrared Spectrum of CH 5 + Revisited. Kyle N. Crabtree , James N. Hodges, and Benjamin J. McCall. Why study CH 5 + ?. Astrochemistry. Quantum Mechanics. Highly symmetric fluxional molecule Challenging to traditional notion of structure. - PowerPoint PPT PresentationTRANSCRIPT
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The Infrared Spectrum of CH5+ Revisited
Kyle N. Crabtree, James N. Hodges, and Benjamin J. McCall
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Why study CH5+?
Astrochemistry
• Formed by radiative association of CH3
+ + H2
• Stable against H2, so might be detectable in interstellar environments
• Potential tracer for CH3+ and
gas-phase CH4, which have no rotational spectrum
• Possible precursor to gas-phase C-C bond formation
Quantum Mechanics
• Highly symmetric fluxional molecule
• Challenging to traditional notion of structure
Courtesy Joel Bowman
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CH5+ structure and dynamics
Z. Jin et al., J. Phys. Chem. A. (2006) 110, 1569-1574A. B. McCoy et al., J. Phys. Chem .A (2004) 108, 4991-4994
Cs(I)120 forms
0 cm-1
Cs(II)120 forms~30 cm-1
C2v
60 forms~300 cm-1
Ground state wavefunction fully delocalized among 120 Cs(I) minimaG240 (S5
*) permutation-inversion symmetry
xkcd.com/55
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The unassigned rovibrational spectrum of CH5+
E. T. White et al., Science (1999) 284, 135-137
Velocity modulation spectroscopyl-N2 cooled H2/CH4 plasmaLine uncertainties 90-180 MHz917 transitions
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Extracting information from an unassigned rovibrational spectrum
• Combination differences give rotational energy level spacings, but no assignment!
• 4-line combination differences (4LCDs)
v=0
v=1
J=1
J=2
J=1
J=2
Q(1) P(2) R(1) Q(2)
DE DE
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Large uncertainties limit 4LCD analysis• Each transition has uncertainty s• Valid 4 LCD means:
• Large s false positives• With 917 observed transitions, total possible 4LCDs:
= 175619245830 (1.8 x 1011)• With 90-180 MHz uncertainty, ~107 4LCDs found• Most of these are likely false positives; require more precise
frequencies
v=0
v=1
J=1
J=2J=1
J=2
Q(1) P(2) R(1) Q(2)
DE DE
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Reducing uncertainties in IR spectroscopy
Optical Frequency Combs Optical Parametric OscillatorsLaser stabilization & frequency
measurement (<10 kHz accuracy)High optical power (1 W) saturation of
rovibrational transitions (linewidth < 50 MHz)Higher bandwidth detectors FM
spectroscopy
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OPO-NICE-OHVMS
Lamb dipsPrecision: ~300 kHz
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Producing CH5+ in a positive column
CH4 (20 mTorr) + H2 (1 Torr), minimum possible plasma current
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First CH5+ detection with NICE-OHVMS
Plasma current ~200 mA (vs. ~80for optimal production)
Challenge: decrease plasma current without increasing technical noise
Neutral H2
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Technical noise at low plasma current
No PlasmaHigh current (40 kHz, 125 mA)Low current (6 kHz, 70 mA)
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Comparison with Oka’s spectrum
Scan DirectionScan rate > detection system time constant?Line center offset, broad lineshape, asymmetry
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Summary
• CH5+ high resolution spectrum remains unassigned
• OPO-NICE-OHVMS allows measurement of IR transitions with sub-MHz accuracy
• 4LCD analysis energy level spacings• Spectral acquisition and calibration in progress
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Acknowledgements
NASA Earth and Space Science Fellowship Program