Spectral taxonomy: A semi-automated combination of chirped- pulse and cavity Fourier transform...
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Transcript of Spectral taxonomy: A semi-automated combination of chirped- pulse and cavity Fourier transform...
Spectral taxonomy: A semi-automated combination of chirped-pulse and cavity Fourier transform microwave spectroscopyKyle N. Crabtree, Marie A. Martin-Drumel, and Michael C. McCarthy
Harvard-Smithsonian Center for Astrophysics
Microwave spectroscopy at the CfA
Microwave spectroscopy of reactive molecules: astrochemistry, atmospheric chemistry, and exotic species
200 molecules detected in 20 yearsCations: HNNO+/NNOH+, H2NCO+
Anions: C4H-, C6H-, C8H-
Radicals: HOCO, HO3, C4H, HC3OExotic: Si3, HOON, CH2OO, HOCOH
Cavity FTMspectrometer
Fourier transform spectrometer (5-26 GHz, 1 MHz bandwidth)
Supersonic expansion discharge nozzle
High sensitivity, high resolution
Dilutegaseous
precursors -HV
CP-FTMW spectrometer
20 GHz, 50 GS/s scope
24 GS/sAWG
+38 dB
+30 dB
18.99 GHzPLDRO
10 MHz RbStandard
LPFilter
0.5-10.5 GHz;4 msec duration
StepAtten
0-70 dB
10 pulses; D 20 mst=0
t 250 ms
• Real-time phase scoring and correction• >1M co-averages routine
Linux DAQsoftware
18.5-8.5 GHz
200W7.5-18 GHz
TWTAData Validity
Monitor
Eccosorb−30 dB
Opportunities and goals Chemical profiling of
reactive gas mixtures with intermediates (Miller-Urey-like experiments)
Conformer, vibrational-state discrimination
Analysis challenges for U-lines: Combine CP and cavity FT spectroscopy
Illustration by Adrian J. Hunter, CC-BY-SA 3.0
Example: C2H2 + CS2 discharge150k gas pulses, 1.5M chirps: ~8.5h @ 5Hz1% C2H2, 1% C2S, 98% Ne1 kV discharge
Example: C2H2 + CS2 discharge
495 features with SNR > 3 Of the strongest 34 features (SNR > 50):
13 artifacts (LO; harmonics; scope spurs) 10 assigned (C3S, c-C3H2, SO2, HC3S, C5S, H2C3S, C2S) 11 unidentified
150k gas pulses, 1.5M chirps: ~8.5h @ 5Hz1% C2H2, 1% C2S, 98% Ne1 kV discharge
Chirped-pulse vs. cavityC
hir
ped
-pu
lse
8.5 h
Chirped-pulse vs. cavityC
hir
ped
-pu
lse
Cavit
y
8.5 h
11 h
Chirped-pulse vs. cavityC
hir
ped
-pu
lse
Cavit
y
8.5 h
11 h
8.5 h
9 s(0.0025 h)
Chirped-pulse vs. cavityC
hir
ped
-pu
lse
Cavit
y
8.5 h
11 h
8.5 h
9 s(0.0025 h)
Bandwidth Intensity accuracy Resolution Frequency accuracy Sensitivity
Bandwidth Intensity accuracy Resolution Frequency accuracy Sensitivity
Chirped-pulse + cavityC
hir
ped
-pu
lse
Cavit
y
Chirped-pulse + cavityC
hir
ped
-pu
lse
Cavit
y
Chirped-pulse + cavityC
hir
ped
-pu
lse
Cavit
y
Automated analysis with cavity
QtFTM: Cavity control software designed for programmatic, automated acquisition
Automated analysis with cavity
Automated analysis with cavity Import list of
frequencies from CP spectrum
Automatically tune cavity to each frequency
Integrate for a duration based on CP intensity
Determine how many lines are present, fit to instrument response function
Remeasure under different conditions (e.g. discharge turned off)
For each line found in CP spectrum, determine if line disappears when conditions change; classify:
Taxonometric classification
Discharge
Magneticfield
Gas 2present
Gas 1present
Buffer gasimpurities
Gas A cmplxor impurity
Gas
B c
mpl
x
or im
purit
y
Close
d-sh
ell
inte
rmed
/pro
d
Open-shell I/P
Example acquisition: Discharge test
Dischargeenabled
Dischargedisabled
Example acquisition: Discharge test
Example acquisition: Discharge test
Example acquisition: Discharge test
Example acquisition: Discharge test
DC DC DC DC DC DC
Taxonomy flowchart
Yes
Yes No
Yes No Yes No
Y N NY Y N Y N
Y N Y N Y N Y NY N Y N Y N Y N
Detected in cavity?
Discharge?
Magnetic?
CS2 only?
C2H2 only?
Taxonomy flowchart
Yes
Yes No
Yes No Yes No
Y N NY Y N Y N
Y N Y N Y N Y NY N Y N Y N Y N
Detected in cavity?
Discharge?
Magnetic?
CS2 only?
C2H2 only?
795 1328 170 0 0 0 0 0 0 3 0 0 0
28 17 102 13 0 0 3 0
45 115 0 3
160 3
163
Non-detections: 330/495 (past expt: 20%)
Taxonometric classification
Discharge
Magneticfield
C2H2
present
CS2
present0
0
0
00
00
395
7
132817
0
Taxonometric classification
Discharge
Magneticfield
C2H2
present
CS2
present0
0
0
00
00
395
7
132817
0
Next step: cross-correlation within groups using double resonance
MW-MW double resonance
fFTM
J = 0
J = 2
J = 1fFTM
MW-MW double resonance
fDR
fFTM
J = 0
J = 2
J = 1fFTM
fDR
MW-MW double resonance
fDR
fFTM
J = 0
J = 2
J = 1fFTM
fDR
MW-MW double resonance
fDR
fFTM
J = 0
J = 2
J = 1fFTM
fDR
DR cross correlation
Discharge
Magneticfield
C2H2
present
CS2
present0
0
0
00
00
395
7
132817
0
For each line, look for DR link at every other (unique) frequency# scans Nlines
2/2
DR cross correlation – C2H2 magnetic
DR cross correlation – C2H2 magnetic
DR cross correlation – C2H2 magnetic
No DR
DR cross correlation – C2H2 magnetic
Link!
DR cross correlation – C2H2 magnetic
8/17 lines: c-C3H2
Remainder: unassigned.No obvious linkages
DR cross correlation – C2H2 magnetic
8/17 lines: c-C3H2
Remainder: unassigned.No obvious linkages
DR cross correlation
Discharge
Magneticfield
C2H2
present
CS2
present0
0
0
00
00
395
7
132818
0
Only the 60 strongest lines are shown in this example
DR cross correlation – CS2 + C2H2 discharge
4: C5S4: C4S2: C3S n5=12: C3S n5=12: C13CCS
Remainder: unassigned.Some linkages are likely unassigned vibrational states of molecules above
DR cross correlation – CS2 + C2H2 discharge
4: C5S4: C4S2: C3S n5=12: C3S n5=12: C13CCS
Remainder: unassigned.Some linkages are likely unassigned vibrational states of molecules above
Spectral taxonomy
Future: 2-26 GHz CP coverage