68 th International Symposium On Molecular Spectroscopy June

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 DEUTERIUM QUADRUPOLE COUPLING IN PROPIOLIC ACID AND FLUOROBENZENES MEASURED WITH FTMW SPECTROMETER USING MULTIPLE FIDS. † Ming Sun Bryan Sargus Spencer J. Carey Stephen G. Kukolich Department of Chemistry University of Arizona † Supported by the National Science Foundation

68 th International Symposium On Molecular Spectroscopy • 1) 2) Testing sensitivity and resolution of 2 Spectrometers Coaxial Beam - with multiple FID’s, 12” mirrors (Cobra) > 10 k. Hz resolution, high sensitivity (TC 05) Large Cavity – 48” mirrors, coaxial beam > 2 k. Hz resolution June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 FTMW Spectrometer Design Homodyne system HP 8673 H Synthesizer 2. 0 -18 GHz +13 d. Bm out ~ NARDA SPDT Switch Adjustable Attenuator Cavity Phase Shifter To RF Detector Mixer Power Divider Miteq 4 -18 GHz LNA SRS Preamplifier SR 560 DC-10 MHz Tektronix TDS 210 or PICOSCOPE 5203 To Oscilloscope

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Mixer To A/D SCOPE Vacuum Chamber To RF Detector 1 -18 GHz Wave Generator SPDT Switch Diffusion Pump

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Gas Line RF Detector Oscilloscope SRS AMP SPDT Switch LNA & Mixer Chamber Attenuator & Phase Shifter BNC 575 Gas Pulse Box PC Diffusion Pump Microwave Synthesizer Power Didivder

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 GAS PULSE BOX 100 us 1 us 20 us Trigger point SCOPE Pure background Good FIDs

68 th International Symposium On Molecular Spectroscopy Background June 17 -21, 2013 10 FIDs × 100 μs /FID × 2 + 1600 μs 1600 μ s delay 10 FIDs

68 th International Symposium On Molecular Spectroscopy SUM OF FID’s MINUS BACKGROUND June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy 1 – FLUOROBENZENE (4 -d) June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Table 1. Observed Transitions of Deuterated 1 -fluorobenzene (4 -d 1) in MHz. J′ Ka ′ Kc ′ F′ J″ Ka ″ Kc ″ F″ nobs no-c 1 0 0 0 0 1 4174. 449 0. 003 1 0 1 2 0 0 0 1 4174. 536 0. 001 1 0 0 0 1 4174. 594 0. 002 S. Jans-Burli, M. Oldani and A. Bauder, Molec. Phys, 68, 1111 (1989).

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 1 -fluorobenzene-4 d 1 1% in Neon 10 shots, 8 FIDs MULTI-FID (1) SPECTROMETER w/ 12” MIRRORS S. Jans-Burli, M. Oldani and A. Bauder, Molec. Phys, 68, 1111 (1989).

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Big spectrometer Hanning window function (2)

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Big spectrometer Gaussian window function (2)

68 th International Symposium On Molecular Spectroscopy DIFLUOROBENZENE – 4 D June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Molecule # lines Frequency Range 1 -fluorobenzene (4 d 1) 3 @ 4174. 5 1, 2 -difluorobenzene (4 -d 1) 35 3. 4 GHz - 11. 7 GHz HCCCOOD 37 5. 0 GHz - 11. 8 GHz DCCCOOH 59 6. 0 GHz - 15. 1 GHz

68 th International Symposium On Molecular Spectroscopy 0. 5% 1, 2 -difluorobenzene-4 d 1 10 shots, 8 FIDs June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Table 5. Spectroscopic Constants of Deuterated 1, 2 difluorobenzene (4 -d 1). a This work a Literature Valuesb A 3234. 83167(92) 3234. 821 B 2147. 68666(57) 2147. 680 C 1290. 58578(57) 1290. 581 DJ 0. 0000794(302) 1. 5χaa 0. 1967(62) 0. 25(χbb- χcc) 0. 0072(34) no. lines 35 91 rms 0. 002 0. 067 Errors are 1 s in the last quoted decimal places.

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 D (C-D) D (O-D)

68 th International Symposium On Molecular Spectroscopy liquid PA-OD (30 C) in 15 psi Ar 1000 shots, 10 FIDs June 17 -21, 2013 R. Wellington, M. C. L. Gerry, J. Molec. Spectr. 59, 407 (1976).

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Table 6. Spectroscopic Constants of Deuterated Propiolic Acid in MHza. DCCCOOH HCCCOOD This work Combined fitb MP 2 A 12110. 01758(217) 12110. 00835(182) 11990 11858. 44934(132) 11858. 44340(199) 11725 B 3819. 67859(110) 3819. 70540(98) 3786 4015. 71252(41) 4015. 71150(101) 3985 C 2899. 60416(55) 2899. 58041(116) 2878 2995. 59587(48) 2995. 59274(99) 2974 DJ 0. 000096(64) 0. 000556(48) 0. 0005205 0. 000365(54) DJK 0. 02296(36) 0. 020202(287) 0. 01891 0. 017466(286) DK -0. 00795(38) -0. 00652(32) -0. 004026 -0. 00457(40) δJ 0. 0001765(140) 0. 0001593 0. 0001294(90) δK 0. 01036(63) 0. 01106 0. 01249(45) 0. 3848(49) 0. 3836(49) 0. 4432 0. 00785(211) 0. 00695(215) 0. 0101 1. 5χaa 0. 3080(40) 0. 3090(40) 0. 25(χbb- χcc) 0. 365 -0. 0585 χab no. lines 59 74 37 57 rms 0. 004 0. 063 0. 001 0. 072 a Errors are 1 s in the last quoted decimal places. b D. G. Lister and J. K. Tyler, Spectrochimica Acta, 28 a, 1423 (1972).

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Table 7. Field gradient related parameter (eq) compared with the stretching force constant (ks) and bond length to hydrogen. Molecule eq. Q_bond (k. Hz) eq (N∙m-1) ks (N∙m-1) Bond Length (Å) Pro-OD 283. 5 a 656. 9 703. 4 d 0. 969 a HCOOD 272. 0 b 630. 2 720. 0 b 0. 972 e Pro-CD 206. 4 a 478. 2 686. 9 d 1. 066 a d. FBz_4 d 1 193. 7 a 448. 7 625. 6 d 1. 080 f m. FBz_4 d 1 187. 7 c 434. 9 613. 9 d 1. 081 g C 6 H 5 D 186. 1 c 431. 2 629. 6 d 1. 082 h DCOOH 166. 0 b 384. 6 470. 0 b 1. 097 e This work. S. G. Kukolich, Mol. Phys. 29, 249 (1975). c S. Jans-Bürli, M. Oldani, and A. Bauder, Mol. Phys. 68, 1111 (1989). d Values estimated by using a simple harmonic oscillator with OD/CD stretching frequencies: for CD stretching, deuterium mass used as the reduced mass; for OD stretching, the reduced mass of O and D used. e G. Kwei and R. Curl, J. Chem. Phys. 32, 1592 (1960). f O. L. Stiefvater, Z. Naturforsch, 43 a, 147 (1988). g Z. Kisiel, E. Bialkowska-Jaworska, L. Pszczólkowski, J. Mol. Spectr. 232, 47 (2005). h M. Oldani and A. Bauder, Chem. Phys. Lett. 108, 7 (1984). a b

68 th International Symposium On Molecular Spectroscopy Acknowledgements • N$F - This material is based upon work supported by the National Science Foundation under Grant Nos. CHE 0809053, CHE-0721505 and CHE 10557796. • RESEARCH CORPORATION “PARTNERS IN SCIENCE” June 17 -21, 2013

68 th International Symposium On Molecular Spectroscopy June 17 -21, 2013 Gas Pulse ~1 ms ~1 us ~200 us Microwave Pulse A/D acquisition