1. Analysis of High Resolution Infrared Spectra of 1,1-Dichloroethylene in the 500 − 1000 cm −1 Range Rebecca A. Peebles, Sean A. Peebles Department of Chemistry Eastern Illinois University 600 Lincoln Ave. Charleston, IL 61920 Daniel A. Obenchain Department of Chemistry Wesleyan University 52 Lawn Avenue Middletown, CT 06459-0180

2. Background Haloethylenes Haloethylenes – Polymer precursors – Potential pollutants Large scale industrial use Large scale industrial use – “Good” rotational constants – Some previous microwave and IR work 2

3. Canadian Light Source Bruker IFS-125HR FTIR spectrometer Bruker IFS-125HR FTIR spectrometer 0.00096 cm -1 resolution 0.00096 cm -1 resolution 2 m cell (up to 72 m path length) 2 m cell (up to 72 m path length) 5 – 1000 cm -1 range using synchrotron 5 – 1000 cm -1 range using synchrotron 3

4. Experimental Details 500 – 1100 cm -1 range 500 – 1100 cm -1 range 72 m path length for all scans 72 m path length for all scans 0.00096 cm -1 resolution 0.00096 cm -1 resolution – Aperture 1.15 mm 80 kHz scan rate 80 kHz scan rate KBr beam splitter and optics KBr beam splitter and optics GeCu detector GeCu detector Three scans: Three scans: – 17 mTorr, 9 mTorr, 35 mTorr Calculations: MP2/6-311++G(2d,2p) Calculations: MP2/6-311++G(2d,2p) – Anharmonic frequencies 4

5. Full Spectrum 5 Frequency / cm -1 b-type C-Cl Sym. Str. 4 b-type C-Cl Sym. Str. 4 a-type C-Cl Asym. Str. 9 a-type C-Cl Asym. Str. 9 c-type CH 2 Wag 11 11 c-type CH 2 Wag 11 11 a-type CH 2 Rock 8 a-type CH 2 Rock 8

6. Ab Initio Calculations a Z. Kisiel, L. Pszczółkowski, Z. Naturforsch, 50a, (1995), 347. 6

7. High Resolution Spectra Frequency / cm -1 17 mTorr, 101 Scans 9 mTorr, 209 Scans 7

8. AABS: Z. Kisiel, L. Pszczolkowski, I. R. Medvedev, M. Winnewisser, F.C.De Lucia, C. E. Herbst, J.Mol.Spectrosc., 233, (2005), 231. PROSPE Web SITE: Z.Kisiel, in: J. Demaison, et al. (Eds.), Spectroscopy from Space, Kluwer Academic Publishers, Dordrecht, 2001, pp.91-106. 8

9. AABS “m” to turn on lineshape profile HWHH = 0.0005 cm -1 Lorentzian lineshapes 9

10. HWHH = 0.0005 cm -1 Lorentzian lineshapes 10

11. Spectroscopic Constants 11

12. Conclusions/What’s Next? 12 F. Winther, D. O. Hummel, Spectrochim. Acta, 23A, (1967), 1839. 4 mm Hg 25 mm Hg 200 mm Hg 80 mm Hg

13. Acknowledgements Dennis Tokaryk Dennis Tokaryk Jennifer van Wijngaarden Jennifer van Wijngaarden Norm Craig Norm Craig Brant Billinghurst Brant Billinghurst Canadian Light Source, Inc. Canadian Light Source, Inc. EIU Council on Faculty Research/Chemistry Department EIU Council on Faculty Research/Chemistry Department Lena Elmuti Lena Elmuti 13

14. 14

15. Vibrational Modes/Symmetry a a b b a a b b c c b b Displacement vectors Dipole derivatives (1) F. Winther, D. O. Hummel, Spectrochim. Acta, 23A, (1967), 1839. (2) E. D’Alessio, E. Silberman, E. A. Jones, J. Mol. Struct., 9, (1971), 393. 15 HELP!

16. 16

17. 17