determination of pressure broadening and shifts for the first overtone 2←0 of hcl brennan m....
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MK10 HCl Overtone Lineshapes 1
DETERMINATION OF PRESSURE BROADENING AND SHIFTS FOR THE FIRST OVERTONE
2←0 OF HCL
Brennan M. Coffey, Brian J. Drouin, Timothy J. Crawford
Jet Propulsion Laboratory, California Institute of Technology
6/16/2014
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MK10 HCl Overtone Lineshapes 2
Motivation• Textbook case
– but precision is not up to modern standards– Last Investigation into the line centers of HCl in the MIR was done by
Guelachvili Opt. Comm. 19(1) 150-154, 1976 line positions to ~2x10-4 cm-1
• Laboratory calibration– Wavenumber calibration for 6000 cm-1 region– Dual scan experiment has allowed transfer of CH4 standard to HCl– Positions may be improved to ~1x10-5 cm-1
• No (bandwide) self broadening or self shift parameters – TCCON calibration, common calibration for networked measurement system– Remote sensing for Venusian / Jovian / Saturnian chemistry
• LabFit exercise– Multispectrum lineshape fitting
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MK10 HCl Overtone Lineshapes 3
Band Selectionhttp://hitran.iao.ru/survey/spectr
4800 5200 5600 6000 cm -1
Pubchemcommons.wikimedia.orghalo.wikia.com
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MK10 HCl Overtone Lineshapes 4
TCCON network
• The Total Carbon Column Observing Network (TCCON) is a network of ground-based Fourier Transform Spectrometers that record direct solar spectra in the near-infrared. From these spectra, accurate and precise column-averaged abundances of atmospheric constituents including CO2, CH4, N2O, HF, CO, H2O, and HDO, are retrieved.
• Calibrations are performed with sealed 10 cm 5mb HCl cells inside each interferometer
• Hase, F., B.J. Drouin, C.M. Roehl, G.C. Toon, P.O. Wennberg, D. Wunch, T. Blumenstock, F. Desmet, D.G. Feist, P. Heikkinen, M. De Maziere, M. Rettinger, J. Robinson, M. Schneider, V. Sherlock, R. Sussmann, Y. Te, T. Warneke, C. Weinzierl, Calibration of sealed HCl cells used for TCCON instrumental line shape monitoring, Atmos. Meas. Tech. 6(12), 3527-3537, 2013.
• ‘Narrowing’ effect is evident in Hase et al.
http://www.tccon.caltech.edu/site-locations/index.htmlhttps://tccon-wiki.caltech.edu/
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MK10 HCl Overtone Lineshapes 5
Remote Sensing of HCl
Venus, solar occultation spectra, http://venus.aeronomie.be/en/soir/hcl.htm
Goto et al.Earth Science:HALOE, ACE, MLS, Odin, ATMOSMk IV, FIRS-2, SLS, (ALIAS in-situ)
Also astronomy with: Spitzer, ISO, ATMOS, Odin, Herschel6/16/2014
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MK10 HCl Overtone Lineshapes 6
IFS-125HR
Bruker IFS-125HR at JPL▪ The entire FTS enclousure evacuated to ~10 mTorr▪ Maximum resolution, 0.0011 cm-1
▪ Detectors and beamsplitters covering 20 - 15800 cm-1
▪ Gas handling system with a 6″ Varian Turbo pump▪ MKS Baratron pressure gauges up to 6.5 bar▪ Hart Scientific PRT temperature sensors
Various absorption gas cells▪ Multipass White cell of (variable path length up to 32.5 m)▪ Cryogenic cell (0.2 m long, developed by Dr. Arlan Mantz) ▪ Various single pass custom cells (from 2 cm to 26.5 cm)▪ Very long path multipass White cell (~200 m) on the way
Pressure scans in a joint
tandem cell at 8 different pressures
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MK10 HCl Overtone Lineshapes 7
Experimental• Two cells were used• Long Path length (3.84 m)• Short Path length (0.0614 m and 0.1526 m)
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MK10 HCl Overtone Lineshapes 8
Calibration strategy• Recent improvements in the metrology of CH4 and C2H2 have made the
desired precision and accuracy attainable• Absolute positions were determined with femtosecond laser spectroscopy
Zolot, 2013
σ (MHz) σ (cm-1)
2.3 7.6E-05
1.0 3.3E-05
1.7 5.6E-05
2.5 8.3E-05
2.4 8.0E-05
1.2 4.0E-05
7.8 2.6E-04
1.3 4.3E-05
0.5 1.6E-05
1.2 4.0E-05
1.5 5.0E-05
0.8 2.6E-05
… …Zolot et al. JQSRT 118 (2013) 26-39
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MK10 HCl Overtone Lineshapes 9
Position• Algorithm Information
– Code in Matlab was written to analyze the spectra for line centers– Thresholding based on a ratio of intensity at the base of the peak and intensity at the
peak was used as filtering criteria• <5% of max intensity was not considered a peak
– Peak picker uses zero filling, apodization, then spline interpolation between the bottom 3 points
– Peak minimum finder based on 5 smoothing points and first and second derivative tests
Position (cm-1)
Resi
dual
s (c
m-1
)
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MK10 HCl Overtone Lineshapes 10
Line CentersNumber Matched Match Threshold Standard Deviation Cal Factor
46 0.00221 0.00007009 1.00000093
40 0.00057 0.00003566 1.00000010
20 0.00012 0.00001120 1.00000003
8 0.00010 0.00000819 1.00000009
• Matched values to the Zolot lines, goal was to improve the calibration error to be <2x10-4 cm-1
• We can get 1x10-5 cm-1, sufficient precision and accuracy for use in OCO spectral analyses
• Precision was verified with quantum mechanical prediction software and had an RMS of ~7x10-6 cm-1
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MK10 HCl Overtone Lineshapes 11
Pressure Broadening• 1st Pressure broadening
and pressure shifts for entire v = 2-0 band
• Spectra taken in a dual chamber cell were used with CH4 in one chamber as the calibrant and HCl in the other
• Pressures investigated were 10,15, 20, 25, 30, 40, 50 and 60 Torr
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MK10 HCl Overtone Lineshapes 12
Spectral Fitting no constraints• Full Physics fits with LabFit to get pressure broadening and pressure shift
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MK10 HCl Overtone Lineshapes 13
Fitting Spectra with constraintsIntensities with Honl-London Factors, exp(hv/kT), positions with B0,B2, D0,D2, H0, H2
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MK10 HCl Overtone Lineshapes 14
Linestrength – HITRAN• On average 2.6%
higher than HITRAN
• Both intensity and pressure broadening are consistently higher than HITRAN
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MK10 HCl Overtone Lineshapes 15
Isotopologues Comparison – Self Broadening
0 2 4 6 8 100
0.05
0.1
0.15
0.2
0.25
0.3
|m|
self
broa
dene
d ha
lfwid
th (c
m-1
/atm
)
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MK10 HCl Overtone Lineshapes 16
Isotopologues Comparison – Self Shift
-7 -5 -3 -1 1 3 5 7 9 11-0.005
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
mse
lf sh
ift (c
m-1
/atm
)
0 2 4 6 8 10-0.005
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
|m|
self
shift
(cm
-1/a
tm)
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The self-shift is not reported in HITRAN, nor any literature, yet it iscritical to precisely calibrate the wavenumber of a spectrometer
using typical HCl absorption pressure-pathlengths.
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MK10 HCl Overtone Lineshapes 17
Isotopologues Comparison – Dicke
0 2 4 6 8 100
0.01
0.02
0.03
0.04
0.05
0.06
|m|
Dick
e pa
ram
eter
-7 -5 -3 -1 1 3 5 7 9 110
0.01
0.02
0.03
0.04
0.05
0.06
m
Dick
e pa
ram
eter
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The narrowing phenomenon is correlated with instrument variables such asresolution and aperture. The multispectrum fitting method allows a consistent
retrieval over many pressures with these instrument variables fixed. The isotopologue comparison highlights the reproducible trend that has been separated
from instrument variables.
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MK10 HCl Overtone Lineshapes 18
Hamiltonian Parameters from constrained fit
G(H35Cl) 5667.9824970 0.31266838505E-05 G(H37Cl) 5663.9268346 0.57468641899E-05 B"(H35Cl) 10.440189334 0.47834078032E-06 B"(H37Cl) 10.424502872 0.10281972891E-05 D"(H35Cl) 0.52805708530D-03 0.12479988598E-07 D"(H37Cl) 0.52645439847D-03 0.39573635036E-07 H"(H35Cl) 0.16600000000D-07 Fixed H"(H37Cl) 0.22900000000D-07 Fixed B'(H35Cl) 9.8345885033D+01 0.43757773938E-06 B'(H37Cl) 9.8202784918D+01 0.10900827192E-05 D'(H35Cl) 0.51541494165D-03 0.87793443626E-08 D'(H37Cl) 0.51416332228D-03 0.29243450328E-07 H'(H35Cl) 0.15400000000D-07 Fixed H'(H37Cl) 0.21300000000D-07 Fixed
SQ/nu(H35Cl) 0.10469429511D-23 0.11154688922E-27 SQ/nu(H37Cl) 0.33157419710D-24 0.57034946781E-28 c1 (H35Cl) -.22686827401D-02 0.10987143469E-04 c1 (H37Cl) -.22476757421D-02 0.21406525775E-04
Guelachvili Opt. Comm. 19(1) 150-154, 1976
C01 = -2.60(27)x10-3, c0
2 = -0.86(57)x10-3
Tipping & Ogilvie JMS. 96 442-450, 1982Toth et al. JMS. 35, 110-126, 1970
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MK10 HCl Overtone Lineshapes 19
Summary and Future Directions• HCl spectra at multiple pressures have been
analyzed simultaneously for lineshape parameters
• Low pressure scan has intensity issues, but should improve accuracy of positions
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MK10 HCl Overtone Lineshapes 20
Acknowledgements
• NASA ACLR• OCO-2 ABSCO• Linda Brown• Keeyoon Sung• Malathy Devi• D. Chris Benner
6/16/2014
© 2014 California Institute of Technology. Government sponsorship acknowledged.
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MK10 HCl Overtone Lineshapes 21
Pressure Broadening – HITRAN
m Self WidthSelf Width
ErrorHITRAN Self
Width
Percent Difference
from HITRAN
-5 0.2088 0.0001 0.213 1.9336
-4 0.2346 0.0001 0.238 1.4042
-3 0.2439 0.0001 0.242 0.7758
-2 0.2366 0.0001 0.229 3.2751
-1 0.22 0.0001 0.213 3.2442
1 0.2131 0.0001 0.201 5.9173
2 0.2246 0.0001 0.215 4.3936
3 0.2299 0.0001 0.224 2.6022
4 0.2223 0.0001 0.218 1.9253
5 0.2016 0.0001 0.197 2.2703
6 0.1752 0.0001 0.169 3.6236
7 0.1484 0.0001 0.139 6.6191
8 0.1269 0.0001 0.111 14.05379 0.108 0.0002 0.096 12.2358
H35Cl
m Self WidthSelf Width
ErrorHITRAN Self
Width
Percent Difference
from HITRAN
-4 0.2323 0.0002 0.238 2.3542
-3 0.2420 0.0002 0.242 0.0041
-2 0.2350 0.0002 0.229 2.5926
-1 0.2178 0.0003 0.213 2.2151
1 0.2109 0.0003 0.201 4.8610
2 0.2229 0.0002 0.215 3.6072
3 0.2277 0.0002 0.224 1.6368
4 0.2200 0.0002 0.218 0.8793
5 0.1994 0.0002 0.197 1.1825
6 0.1733 0.0002 0.169 2.5010
7 0.1469 0.0003 0.139 5.5937
8 0.1254 0.0004 0.111 12.7785
9 0.1082 0.0006 0.096 12.4713
H37Cl
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MK10 HCl Overtone Lineshapes 22
Linestrength – HITRANm Intensity
HITRAN intensity Difference
percent difference
-5 6.66E-21 6.38E-21 2.83E-22 4.44
-4 8.83E-21 8.44E-21 3.93E-22 4.66
-3 9.90E-21 9.46E-21 4.47E-22 4.73
-2 8.93E-21 8.53E-21 4.05E-22 4.74
-1 5.46E-21 5.21E-21 2.45E-22 4.71
1 6.02E-21 5.75E-21 2.71E-22 4.71
2 1.09E-20 1.04E-20 4.84E-22 4.66
3 1.33E-20 1.27E-20 5.95E-22 4.69
4 1.31E-20 1.25E-20 5.78E-22 4.62
5 1.09E-20 1.04E-20 4.80E-22 4.61
6 7.90E-21 7.54E-21 3.54E-22 4.70
7 5.02E-21 4.80E-21 2.20E-22 4.59
8 2.83E-21 2.71E-21 1.20E-22 4.42
9 1.42E-21 1.37E-21 5.99E-23 4.39
m IntensityHITRAN intensity Difference
percent difference
-4 2.79E-21 2.69E-21 1.02E-22 3.79
-3 3.13E-21 3.02E-21 1.19E-22 3.93
-2 2.83E-21 2.72E-21 1.11E-22 4.08
-1 1.72E-21 1.66E-21 6.32E-23 3.81
1 1.90E-21 1.83E-21 7.17E-23 3.92
2 3.44E-21 3.31E-21 1.36E-22 4.12
3 4.21E-21 4.05E-21 1.60E-22 3.94
4 4.14E-21 3.98E-21 1.56E-22 3.90
5 3.46E-21 3.32E-21 1.31E-22 3.95
6 2.50E-21 2.41E-21 8.77E-23 3.64
7 1.59E-21 1.54E-21 5.39E-23 3.51
8 8.96E-22 8.68E-22 2.83E-23 3.26
9 4.55E-22 4.37E-22 1.81E-23 4.15
H35Cl H37Cl
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MK10 HCl Overtone Lineshapes 23
Isotopologues Comparison – Line strengthsPoint Ratio
2 3.16
3 3.16
4 3.16
5 3.17
6 3.16
7 3.17
8 3.16
9 3.16
10 3.15
11 3.17
12 3.16
13 3.16
14 3.12
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