Spectral taxonomy: A semi-automated combination of chirped ...

A SEMI-AUTOMATED COMBINATION OF CHIRPED-PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY Kyle N. Crabtree, Department of Chemistry, The University of California, Davis Marie-Aline Martin-Drumel and Michael C. McCarthy, Harvard-Smithsonian Center for Astrophysics Sydney A. Gaster, Taylor M. Hall, Deondre L. Parks, and Gordon G. Brown, Coker College Microwave spectroscopy at the CfA and Coker Center for Astrophysics Microwave spectroscopy of reactive molecules: astrochemistry, atmospheric chemistry, and exotic species Coker Microwave spectroscopy of stable molecules and complexes. Training undergraduate students. Analysis and Assignment of Microwave Spectra

At research institutions: a bottleneck in experimental process At teaching institutions: a challenge for undergraduate students Two approaches to simplify analysis and assignment: Computational Autofit Steve Shipman (NCF) and Brooks Pate (UVA)

Evolutionary Algorithm Leo Meerts (Radboud University) Experimental Semi-automated Combination of CP-FTMW and c-FTMW spectroscopies (this talk) Spectral taxonomy CP-FTMW Kyle Crabtree RE03 2014 Simple Test Case 3,4-difluorobenzaldehyde cis-3,4-dFB TOT = 3.3 D trans-3,4-dFB TOT = 0.6 D How far in experiment can we get without thinking???

Semi-Automated Combination of Cavity and CP-FTMW Spectroscopy Measure CP-FTMW spectrum (8 18 GHz) Deep averaging (> 1M shots) Use cavity-FTMW spectroscopy to aid analysis Check lines at various attenuations High-resolution measurement Information regarding dipole moment of conformer

Double-resonance experiments Discover connectivity of transitions Aid in assignment of quantum numbers CP-FTMW spectrometer 0.5-10.5 GHz; 4 msec duration 24 GS/s AWG 10 pulses; D 20 ms t=0 LP Filter t 250 ms

18.5-8.5 GHz Step Atten +30 dB 0-70 dB 10 MHz Rb Standard 18.99 GHz PLDRO Data Data Validity Validity Monitor Monitor +38 dB 20 GHz, 50 GS/s scope

Linux DAQ software 30 dB Eccosorb Real-time phase scoring and correction >1M co-averages routine 200W 7.5-18 GHz TWTA c-FTMW spectrometer Fourier transform spectrometer (5-26 GHz, 1 MHz bandwidth) Supersonic expansion discharge nozzle

High sensitivity, high resolution MW-MW double resonance fFTM J=2 fFTM J=1 J=0 MW-MW double resonance fFTM fDR fDR fFTM J=2 J=1 J=0

MW-MW double resonance fFTM fDR fDR fFTM J=2 J=1 J=0 CP-FTMW Spectrum 9.2 million averages (approx. 50 hours) CP-FTMW Spectrum 9.2 million averages (approx. 50 hours) 3,4-dFB CP-FTMW Spectrum 9.2 million averages (approx. 50 hours) 3,4-dFB

x 100 CP-FTMW Spectrum 9.2 million averages (approx. 50 hours) 3,4-dFB x 100 18 O Automated analysis with cavity Batch file check 706 lines at 2 different attenuations 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 Fit cavity data to frequency Re-measure under different conditions (e.g. attenuation,

etc.) cavity-FTMW Batch file output MW-MW Double Resonance Picked the 119 most intense lines in spectrum Created batch file to measure DR linkages between all possible combinations ~12 hours measurement time MW-MW Double Resonance MW-MW Double Resonance

MW-MW Double Resonance No DR MW-MW Double Resonance Link! MW-MW Double Resonance Output file Quickly find linkages between transitions Analyzing DR - connectivity low level (6_311+g(d,p)) ab initio calculation

selected 32 most intense transitions color coded connected transitions DR - connectivity Assigned lines based on connectivity Ran a few assignments in SPFIT cis-dFB spectrum fit! trans-dFB assignment

Subtracted all cis-dFB lines from spectrum Picked the 45 most intense lines remaining Performed double-resonance batch on the trans lines Found links and assigned spectrum Spectroscopic Parameters - dFB Rotational Parameters A (MHz) B (MHz) C (MHz) J (kHz)J (kHz) J (kHz)JK (kHz) J (kHz)K (kHz) J (kHz)J (kHz) 28 cis Species B3LYP/ Experiment 6311+ al

+g(d,p) 2776.3582 2773.1544 (4) 902.8507 898.8536 (2) 681.4109 678.8275 (1) 0.0206 0.0219(8) -0.0015 0.018(3) 0.39 0.39(1) 0.0060 0.0057 (3) trans Species B3LYP/ 6311+ Experimental +g(d,p)

3028.5880(4 3023.6936 ) 848.4962 851.7309(1) 662.5689 664.8928(1) 0.0121 0.0748 0.456 0.00282 0.032(1) -0.28(1) 0.0104(3) 0.50(3) J (kHz)K (kHz) 0.065

0.065(8) 0.0655 N - 179 - OMC (MHz) - 0.00999 - Inertial Defect (amu*A2)

-0.000058 -0.1231(2) -0.000002 133 0.00962 -0.1338(1) CP-FTMW Spectrum 9.2 million averages (approx. 50 hours) cis-3,4-dFB 322 - 211 18 O Rotational and Distortion Constants of 3,4difluorobenzaldehyde Spectroscopic Parameters cis-dFB

Rotationa Normal l Specie Params s 2776.3 A (MHz) 582 (4) 902.85 B (MHz) 07 (2) C (MHz) J (kHz)J (kHz) J (kHz)JK (kHz) J (kHz)K (kHz) J (kHz)J (kHz) J (kHz)K (kHz) N OMC (MHz) Inertial Defect (amu*A2)

30 681.41 09 (1) 13 C_1 2773.23 61 (2) 899.307 20 (9) 679.203 64 (6) 13 C_2 13 C_3

13 C_4 13 C_5 13 C_6 13 C_7 18 O 2767.52 23 (1) 901.748 98 (9)

2765.73 45 (1) 902.413 97 (9) 2774.48 02 (2) 900.294 8 (1) 2738.521 6 (1) 902.2419 2 (8) 2735.64 97 (1) 901.891 75 (7) 2774.921 4(1) 890.8505

1 (8) 2762.09 08(2) 867.353 2 (1) 680.250 90 (8) 680.522 52 (7) 679.842 0 (1) 678.7629 1 ( 7) 678.388 39 (5) 674.4690

9 (6) 660.182 9 (1) [0.0219] [0.0219] [0.0219] [0.0219] [0.0219] [0.018] [0.018] [0.018] [0.018] [0.018]

[0.39] [0.39] [0.39] [0.39] [0.39] [0.0057] [0.0057] [0.0057] [0.0057] [0.0057] [0.065] [0.065]

[0.065] [0.065] [0.065] 61 0.00413 4 0.1226(4 ) 57 0.0219 [0.0219 [0.0219] [0.0219] (8) ] 0.018( [0.018] [0.018]

[0.018] 3) 0.39(1) [0.39] [0.39] [0.39] 0.0057 [0.0057 [0.0057] [0.0057] (3) ] 0.065( [0.065] [0.065] [0.065] 8) 179 63 54 60 0.0099 0.00597 0.00511 0.00593 9 5

5 3 0.1231( 0.12339( 0.1235( 0.1250(1 9) 1) ) 2) 59 52 0.00728 0.004763 1 0.12503( 0.1239(1) 1) 36 0.00500 0.004703 5 0.12418(8 0.1242(1 ) )

2-Fluoropyridine CO2 complex 2-Fluoropyridine CO2 complex Rotational Parameters Species B3LYP/ 6311+ +g(d,p) A (MHz) 2309.0236 B (MHz) C (MHz) J (kHz)J (kHz) J (kHz)JK (kHz) J (kHz)K (kHz) 781.34093 583.79396

-0.0004228 -0.001010 0.0004937 0.000104791 70 -0.00122476 -6.76012 J (kHz)J (kHz) J (kHz)K (kHz) 3/2 aa (MHz) bb cc (MHz) N OMC (MHz) Inertial Defect (amu*A2) 32 Experiment al 2330.7001(

3) 826.2807(1) 610.8178(1) 0.292(1) 1.010(4) -0.23(1) 0.0724(5) 0.99(1) -6.296(4) -0.28578 -0.294(1) - 208 0.00676 0.024114 -1.0859(2) Future Work

c-FTMW Spectroscopy Software upgrades Search for isotopologues of trans-dFB and 2-Fpyr-CO2 Fully automate transition from CP-FTMW to c-FTMW experiments Algorithm for translating DR data into spectral assignments Coker College Spectroscopy Group

Implement c-FTMW spectroscopy to complement CPFTMW spectroscopy Thanks Mike McCarthy Laboratory Marie-Aline Martin-Drumel Carrie Womack Paul Antonucci Coker students Sydney A. Gaster Taylor M. Hall Deondre L. Parks

Structural Parameters cis-dFB Atoms Bonde d Bond Length (Experimental ) B3LYP/ 6311+ +g(d,p) C1-C2 1.3458 1.3971 C2-C3 1.2596

1.3780 C3-C4 1.4092 1.4021 C4-C5 1.3975 1.3977 C5-C6 1.3855 1.3923 C6-C1 1.3941

1.3852 C4-C7 1.4886 C7-O 1.2093 Atoms Bonded Bond Angle (Experiment al) B3LYP/ 6311+ +g(d,p) C1-C2-C3 132.3795

120.5010 1.4811 C2-C3-C4 113.8290 119.1191 1.2098 C3-C4-C5 120.2158 120.1580 C4-C5-C6 120.1588 120.4546

C5-C6-C1 118.4531 118.8655 C6-C1-C2 114.9580 120.9018 C3-C4-C7 120.5025 120.0730 C4-C7-O 124.1215 124.7265

Table 2: Dipole Moments of 3,4difluorobenzaldehyde Dipole moment cis trans A -0.41 0.60 B 3.25 0.21 C 0.00

0.00 TOT 3.27 0.63 Chirped-pulse Chirped-pulse vs. cavity 8.5 h Chirped-pulse Chirped-pulse vs. cavity 8.5 h Cavity 11 h Cavity

Chirped-pulse Chirped-pulse vs. cavity 8.5 h 8.5 h 11 h 9s (0.0025 h) Chirped-pulse Chirped-pulse vs. cavity 8.5 h Cavity 11 h 8.5 h

Bandwidth Intensity accuracy Resolution Frequency accuracy Sensitivity Bandwidth 9s (0.0025 h) Intensity accuracy Resolution Frequency accuracy Sensitivity Cavity Chirped-pulse Chirped-pulse + cavity Cavity

Chirped-pulse Chirped-pulse + cavity Cavity Chirped-pulse Chirped-pulse + cavity

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