1. Vibrationally Mediated Bimolecular Reactions Christopher J. Annesley University of Wisconsin - Madison

2. Comparing Reactivities of Different Vibrational States in CH 3 D Christopher J. Annesley University of Wisconsin - Madison

3. How do vibrations affect reactions?

14. CH 3 D( 1 or 4 ) + Cl S. Yoon, R. Holiday, E. Sibert III, and F. Crim J. Chem. Phys. 119, 9568 (2003)

15. CH 3 D( 1 or 4 ) + Cl S. Yoon, R. Holiday, E. Sibert III, and F. Crim J. Chem. Phys. 119, 9568 (2003)

16. Antisymmetric Stretch, 4 Symmetric Stretch, 1 CH 3 D( 1 or 4 ) + Cl

17. Antisymmetric Stretch, 4 Symmetric Stretch, 1 CH 3 D( 1 or 4 ) + Cl

18. Antisymmetric Stretch, 4 Symmetric Stretch, 1 CH 3 D( 1 or 4 ) + Cl

19. Antisymmetric Stretch, 4 Symmetric Stretch, 1 CH 3 D( 1 or 4 ) + Cl

20. Antisymmetric Stretch, 4 Symmetric Stretch, 1 CH 3 D( 1 or 4 ) + Cl

22. Product Distributions

23. Action Spectra C. Annesley, A. Berke and F. F. Crim J. Phys. Chem. A submitted

24. Fitting constants Lutz, B. L.; De Bergh, C.; Maillard, J. P. Astrophysical Journal 1983, 273, 397.

25. Action spectra

27. CH 3 D(ν) + Cl Holiday, R. J.; Kwon, C. H.; Annesley, C. J.; Crim, F. F. J. Chem. Phys. 2006, 125, 133101.

28. CH 3 D(ν) + Cl Holiday, R. J.; Kwon, C. H.; Annesley, C. J.; Crim, F. F. J. Chem. Phys. 2006, 125, 133101.

30. State Mixing? A exp A calc B exp B calc ζ exp ζ calc ν1+ν2ν1+ν2 5.1745.1573.8603.790 ν2+ν4ν2+ν4 5.2235.2033.8033.7880.084.24 1 ν 2 +2ν 5 5.2515.2743.9903.843 Herzberg, G. Molecular Spectra and Molecular Structure: II. Infrared and Raman Spectra of Polyatomic Molecules; Van Nostrand Reinhold Co.: New York, 1945.

31. Summary Different vibrations react differently –Products Spectator model –Reactivities Highly mixed states obscure these differences Need new systems to find more examples CH 3 F, CH 2 F 2

32. Thanks NSF