CHIRPED PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE CPFTMW

CHIRPED PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE (CP-FTMW AND FTMW) SPECTRUM OF BROMOPERFLUOROACETONE NICHOLAS FORCE, DAVID JOSEPH GILLCRIST, CASSANDRA C. HURLEY, FRANK E MARSHALL, NICHOLAS A. PAYTON, THOMAS D. PERSINGER, N. E. SHREVE, and G. S. GRUBBS II WJ 08, International Symposium on Molecular Spectroscopy 69 th Meeting - Champaign-Urbana, Illinois

Outline • Driving Force • Background • Theory • Experimental Methods • Setting Up Laboratory • Data and Results • Future Work

Driving Force • To put the bromoperfluoroacetone species into context with other perfluoroacetone/perfluorohexanone derivatives 1, 2 • To further our understanding of the “wet-dog” tunneling motion or Bistrifluoromethyl effect led by S. A. Cooke and coworkers. 3, 4 1. J. -U. Grabow, N. Heineking, and W. Stahl. Z. Naturforsch. 46 a (1991) 229. 2. G. Kadiwar, C. T. Dewberry, G. S. Grubbs II and S. A. Cooke. RH 11, 65 th ISMS (2010). 3. G. S. Grubbs II, Stewart E. Novick, W. C. Pringle, Jr. , Jaan Laane, Esther J. Ocola, and S. A. Cooke. Journal of Physical Chemistry A. 116 (2012) 8169. 4. W. C. Bailey, R. K. Bohn, G. S. Grubbs II, Z. Kisiel, S. A. Cooke. MH 05, 68 th ISMS (2013).

Background - Perfluoroacetone A = 2181. 71980(14) MHz B = 1037. 22930(7) MHz C = 934. 89233(8) MHz

Background - Perfluoroacetone

Background - Chloroperfluoroacetone Parameter 35 -Cl 37 -Cl A 1770. 54709(61) 1753. 6359(18) B 852. 96221(45) 841. 6904(12) C 816. 40819(59) 804. 8988(11) DJ 0. 0774(24) 0. 0787(58) DJK -0. 075(11) -0. 086(33) DK 0. 181(14) 0. 247(94) d. J 0. 0143(15) 0. 0184(29) d. K 0. 75(16) 0. 73(39) caa 13. 206(24) 9. 413(37) cbb -15. 011(32) -14. 430(49) ccc 1. 805(21) 5. 017(32) cab -32. 6(70) -34. 0(97) cac -31. 8(72) -16(21) cbc -43. 89(57) -33. 0(11) N 326 (J = 3 to 12) 170 (J = 3 to 10) rms 0. 0051 0. 0060

Theory Parameter Value A /MHz 1449. 2 B /MHz 632. 9 C /MHz 591. 0 a dipole 1. 39 D b dipole -1. 14 D c dipole -0. 34 D Calculations made at the MP 2/6 -311++G level on the Gaussian 03®, Revision C. 1 suite

Experimental Methods • FTMW spectrometer from Oxford University to date, CP-FTMW planned • Purchased directly from Syn. Quest Labs® and used without further purification • Bubbled Ar at ≈2 atm through sample in a “U”shaped tube in ice ≈40 cm upstream from nozzle

Setting Up Laboratory • FTMW purchased from Oxford University was first to arrive • We have now successfully reconstructed this FTMW spectrometer with all software

Setting Up Laboratory Mark Stephen Snow, Spectroscopic Investigations of Chiral and Induced Chiral Interactions. 2006 Ph. D Thesis for Oxford University.

Results and Data • Used theoretical constants in SPCAT 1 and AABS 2 to predict and sort where to start search on FTMW while CP-FTMW was being constructed • Search started in the 10999 -11021 MHz region where there are predicted many J = 9 – 8, a-type transitions 1. H. M. Pickett, J. Mol. Spectrosc. 148, 371 (1991). 2. Z. Kisiel, L. Pszczolkowski, I. R. Medvedev, M. Winnewisser, F. C. De Lucia, E. Herbst, J. Mol. Spectrosc. 233, 231 -243(2005)

Results and Data • Doppler split transitions found and gasdependent! (all spectra ≤ 500 nozzle pulses)

Future Work • CP-FTMW Run for Less Sample Consumption • Collect More Spectra • Fit and Assign Remaining Spectra • Continue to Setup Laboratory

Acknowledgements • Startup funds from MS&T • University of Missouri System Research Board Grant • Pete Pringle, Stew Novick, Steve Cooke, Brian Howard, and Jens-Uwe Grabow