1. 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 WJ08, International Symposium on Molecular Spectroscopy 69th Meeting - Champaign-Urbana, Illinois

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

3. 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. 46a (1991) 229. 2.G. Kadiwar, C. T. Dewberry, G. S. Grubbs II and S. A. Cooke. RH11, 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. MH05, 68 th ISMS (2013).

4. Background - Perfluoroacetone A = 2181.71980(14) MHz B = 1037.22930(7) MHz C = 934.89233(8) MHz

5. Background - Perfluoroacetone

6. Background - Chloroperfluoroacetone Parameter35-Cl37-Cl A1770.54709(61)1753.6359(18) B852.96221(45)841.6904(12) C816.40819(59)804.8988(11) JJ 0.0774(24)0.0787(58)  JK -0.075(11)-0.086(33) KK 0.181(14)0.247(94) JJ 0.0143(15)0.0184(29) KK 0.75(16)0.73(39)  aa 13.206(24)9.413(37)  bb -15.011(32)-14.430(49)  cc 1.805(21)5.017(32)  ab -32.6(70)-34.0(97)  ac -31.8(72)-16(21)  bc -43.89(57)-33.0(11) N326 (J = 3 to 12)170 (J = 3 to 10) rms0.00510.0060

7. Theory ParameterValue A /MHz1449.2 B /MHz632.9 C /MHz591.0 a dipole1.39 D b dipole-1.14 D c dipole-0.34 D Calculations made at the MP2/6-311++G level on the Gaussian03®, Revision C.1 suite

8. Experimental Methods FTMW spectrometer from Oxford University to date, CP-FTMW planned Purchased directly from SynQuest 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

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

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

11. 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)

12. Results and Data Doppler split transitions found and gas- dependent! (all spectra ≤500 nozzle pulses)

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

14. 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