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2-cyclohexen-1-one (2CHO)

O. 2-cyclohexen-1-one (2CHO). 1. 2. O. O. O. Solution-Phase Photochemistry. h n. O. O. O. Solution-Phase Photochemistry. h n. S 0. h n. S 1 ( n, p *) T 1,2 → products. O. O. O. O. Solution-Phase Photochemistry. h n. S 0. h n. S 1 ( n, p *) T 1,2 → products. O. O. O. O.

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2-cyclohexen-1-one (2CHO)

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  1. O 2-cyclohexen-1-one (2CHO) 1 2

  2. O O O Solution-Phase Photochemistry hn

  3. O O O Solution-Phase Photochemistry hn • S0 hn S1(n,p*)T1,2→products O

  4. O O O Solution-Phase Photochemistry hn • S0 hn S1(n,p*)T1,2→products O

  5. O O O Solution-Phase Photochemistry hn • S0 hn S1(n,p*)T1,2→products S0 → T1(n,p*) viaCRD Spectroscopy

  6. O O O Solution-Phase Photochemistry hn • S0 hn S1(n,p*)T1,2→products ~S2(p,p*) S0 → T1(n,p*) viaCRD Spectroscopy

  7. C C C O T1(n,p*) p* n O C C C C C C C C C p p

  8. S1(n,p*) 1500 cm-1 T1(n,p*) 385 nm 407 nm S0

  9. Telescope Dye Laser 355 nm 407 nm, 2-5 mJ/pulse PMT Ringdown Cell exp (-kt ) Nd:YAG Laser 10 Hz fitter photon loss 100 W l Fast A/D Card CRD Spectrum

  10. Photon loss per pass (parts per thousand) 1

  11. 122 Absorption 99 1

  12. 3902 3930 3901 3910 000 3920 122 Absorption 99 1

  13. 3902 3930 3901 3910 000 3920 122 n39(?) Absorption 99 1

  14. 0.1 Torr 0.3 Torr 1.6 Torr 1

  15. 94.5 cm-1 000 (?) 3910 99.6 cm-1 T1(n,p*) S0

  16. 94.5 cm-1 12 cm-1 7 cm-1 99.6 cm-1 T1(n,p*) S0

  17. 94.5 cm-1 3901 000 99.6 cm-1 T1(n,p*) S0

  18. 94.5 cm-1 3901 93.7 cm-1 000 99.6 cm-1 3910 T1(n,p*) S0 98.6 cm-1

  19. 94.5 cm-1 93.7 cm-1 3901 000 3910 99.6 cm-1 T1(n,p*) S0 98.6 cm-1

  20. 94.5 cm-1 93.7 cm-1 3901 000 3910 99.6 cm-1 98.6 cm-1

  21. 94.5 cm-1 93.7 cm-1 3901 000 3910 99.6 cm-1 98.6 cm-1

  22. 94.5 + 93.6 = 188.1 cm-1 3902 3401 3810 3901 99.6 + 98.4 = 198.0 cm-1

  23. 3902 3901 98.4 cm-1 000 99.6 cm-1

  24. 262.2 cm-1 3801 3902 3901 98.4 cm-1 000 99.6 cm-1

  25. 262.2 cm-1 3801 n38(?) S0: 248.1 cm-1 3902 3901 98.4 cm-1 000 99.6 cm-1

  26. 262.214.1 = 248.1 cm-1 = n38 3811 3801 3902 3901 98.4 cm-1 000 99.6 cm-1

  27. 262.214.1 = 248.1 cm-1 = n38 3811 38113901 3801 99.3 cm-1 3902 3901 98.4 cm-1 000 99.6 cm-1

  28. 244.611.9 = 232.7 cm-1 = n38 3801 3811 38113901 3902 94.3 cm-1 3901 93.6 cm-1 000 94.5 cm-1

  29. 345.4 cm-1 262.2 cm-1 215.5 cm-1 3401 C=O ip wag 3801 3701 C=C twist 3901 000 99.6 cm-1

  30. 345.4 cm-1 34013810 3901 3401 C=O ip wag 34013710 3901 3411 3902 34013710 98.4 cm-1 000 99.6 cm-1

  31. Fundamental Frequencies (cm-1) T1(n,p*) S0 S1(n,p*) 99.6 n39 99.0 122.1 262.2 n38 248.1 251.9 215.5 n37C=C twist 304.1 303.3 345.4 n34C=O wag 485 343.9

  32. Acknowledgements • NSF-RUI (CHE-0848615) • Henry Dreyfus Teacher-Scholar Award • UW-Eau Claire Office of Research and Sponsored Programs

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