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Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. Kaiser Department of Chemistry University of Hawai’i Honolulu, HI 96822

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Presentation on theme: "Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. Kaiser Department of Chemistry University of Hawai’i Honolulu, HI 96822"— Presentation transcript:

1 Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. Kaiser Department of Chemistry University of Hawai’i Honolulu, HI 96822 kaiser@gold.chem.hawaii.edu http://www.chem.hawaii.edu/Bil301/welcome.html Reaction Dynamics in the C( 3 P) + C 2 H 2 (X 1  g + ) System

2 Introduction c-C 3 H(X 2 B 2 ) l-C 3 H(X 2  ) Science, 274, 1508 (1996) 8.8, 28, 45 kJmol -1

3 Introduction l-C 3 (X 1  g + ) + H 2 (X 1  g + )  R G = - 124 kJmol -1 relative energy, kJmol -1

4 Introduction l-C 3 (X 1  g + ) + H 2 (X 1  g + ) Faraday Discussions 119, 27 (2001) Faraday Discussions 119, 51 (2001) Mebel et al. JACS 120, 5751 (1998)  C 3 formation via ISC

5 Introduction relative energy, kJmol -1

6 Open Questions

7 C2H2C2H2 903  316.0  0.3 -- C( 3 P)/Ne 1063  104.9  0.38.0  0.161.5  0.3 C( 3 P)/He 2037  254.9  0.220.4  0.443.8  0.4 C( 3 P)/He 2581  282.9  0.130.7  0.637.2  0.4 13 C 2 H 2 890  516.0  0.3 -- C( 3 P)/Ne 1057  215.0  0.38.0  0.263.0  0.6 C( 3 P)/He 1950  184.4  0.119.3  0.346.8  0.4 C( 3 P)/He 2537  393.3  0.130.4  0.939.3  0.6 C2D2C2D2 890  516.0  0.3 -- C( 3 P)/Ne 1059  124.9  0.38.0  0.163.0  0.4 C( 3 P)/He 1978  145.1  0.219.8  0.346.4  0.4 C( 3 P)/He 2566  373.3  0.131.0  0.839.0  0.6 C 2 HD 890  516.0  0.3 -- C( 3 P)/Ne 1080  105.1  0.38.1  0.161.7  0.4 C( 3 P)/He 1976  175.3  0.219.5  0.345.4  0.4 C( 3 P)/He 2566  453.2  0.230.6  1.038.0  0.7 beamv p, ms -1 SE C, kJmol -1  CM 37 36 39 38 36 38 37 36 m/z

8 13

9

10 C( 3 P) + C 2 D 2 (X 1  g + ) c-C 3 D(X 2 B 2 ) + D( 2 S)  R G = - 2 kJmol -1 l-C 3 D(X 2  ) + D( 2 S)  R G = + 8 kJmol -1 l-C 3 (X 1  g + ) + D 2 (X 1  g + )  R G = - 126 kJmol -1 c-C 3 (X 3 A 2 ’ ) + D 2 (X 1  g + )  R G = - 43 kJmol -1 Ochsenfeld et al. JCP 106, 4141 (1997) Mebel et al. CPL 360, 139 (2002)

11 C2H2C2H2 903  316.0  0.3 -- C( 3 P)/Ne 1063  104.9  0.38.0  0.161.5  0.3 C( 3 P)/He 2037  254.9  0.220.4  0.443.8  0.4 C( 3 P)/He 2581  282.9  0.130.7  0.637.2  0.4 13 C 2 H 2 890  516.0  0.3 -- C( 3 P)/Ne 1057  215.0  0.38.0  0.263.0  0.6 C( 3 P)/He 1950  184.4  0.119.3  0.346.8  0.4 C( 3 P)/He 2537  393.3  0.130.4  0.939.3  0.6 C2D2C2D2 890  516.0  0.3 -- C( 3 P)/Ne 1059  124.9  0.38.0  0.163.0  0.4 C( 3 P)/He 1978  145.1  0.219.8  0.346.4  0.4 C( 3 P)/He 2566  373.3  0.131.0  0.839.0  0.6 C 2 HD 890  516.0  0.3 -- C( 3 P)/Ne 1080  105.1  0.38.1  0.161.7  0.4 C( 3 P)/He 1976  175.3  0.219.5  0.345.4  0.4 C( 3 P)/He 2566  453.2  0.230.6  1.038.0  0.7 beamv p, ms -1 SE C, kJmol -1  CM 37 36 39 38 36 38 37 36 m/z

12

13 Crossed Molecular Beams Setup

14 C( 3 P) + C 2 H 2 (8 kJmol -1 ; m/z = 37) C3HC3H C4HC4H (usec)

15 C( 3 P) + C 2 H 2 (8 kJmol -1 ; m/z = 36) C3HC3H C4HC4H C 3 (R) C 3 (E) (usec)

16 C( 3 P) + C 2 H 2 (20.4 kJmol -1 ; m/z = 37) C3HC3H C4HC4H (usec)

17 C( 3 P) + C 2 H 2 (20.4 kJmol -1 ; m/z = 36) C3HC3H C4HC4H C3HC3H C4HC4H C 3 (R) C 3 (E) (usec)

18 C( 3 P) + C 2 H 2 (30.7 kJmol -1 ; m/z = 37) C3HC3H C4HC4H (usec)

19 C( 3 P) + C 2 H 2 (30.7 kJmol -1 ; m/z = 36) C3HC3H C4HC4H C3HC3H C4HC4H C 3 (R) C 3 (E) (usec)

20 C( 3 P) + C 2 H 2 m/z = 37m/z = 36 C3HC3H C4HC4H C 3 (R) C 3 (E)

21 C( 3 P) + 13 C 2 H 2

22 m/z = 39m/z = 38 C3HC3H C4HC4H C 3 (R) l-C 3 (X 1  g + ) + H 2 (X 1  g + )

23 C( 3 P) + C 2 H 2 / 13 C 2 H 2 C 3 H// 13 C 2 CH C( 3 P)  H 13 C 2 C C( 3 P)  H 2

24 C( 3 P) + C 2 H 2 / 13 C 2 H 2

25 Summary

26 C2H2C2H2 903  316.0  0.3 -- C( 3 P)/Ne 1063  104.9  0.38.0  0.161.5  0.3 C( 3 P)/He 2037  254.9  0.220.4  0.443.8  0.4 C( 3 P)/He 2581  282.9  0.130.7  0.637.2  0.4 13 C 2 H 2 890  516.0  0.3 -- C( 3 P)/Ne 1057  215.0  0.38.0  0.263.0  0.6 C( 3 P)/He 1950  184.4  0.119.3  0.346.8  0.4 C( 3 P)/He 2537  393.3  0.130.4  0.939.3  0.6 C2D2C2D2 890  516.0  0.3 -- C( 3 P)/Ne 1059  124.9  0.38.0  0.163.0  0.4 C( 3 P)/He 1978  145.1  0.219.8  0.346.4  0.4 C( 3 P)/He 2566  373.3  0.131.0  0.839.0  0.6 C 2 HD 890  516.0  0.3 -- C( 3 P)/Ne 1080  105.1  0.38.1  0.161.7  0.4 C( 3 P)/He 1976  175.3  0.219.5  0.345.4  0.4 C( 3 P)/He 2566  453.2  0.230.6  1.038.0  0.7 beamv p, ms -1 SE C, kJmol -1  CM 37 36 39 38 36 38 37 36 m/z

27 Ionization Potentials of C 3 H Isomers C2H2C2H2 C3HC3H Chemical Dynamics Beamline Advanced Light Source L. Belau, S. Leone, M. Ahmed, R.I. Kaiser

28 C3HC3H C4HC4H C4H2C4H2 C6H2C6H2

29 B. Braams J. Bowman Ionization Potentials IP(l-C 3 H) = 9.06 eV IP(c-C 3 H) = 9.66 eV  0.1 eV Experiments* IP(l-C 3 H) = 9.1 eV IP(c-C 3 H) = 9.6 eV  0.1 eV *L. Belau S. Leone M. Ahmed R.I. Kaiser

30 Acknowledgements Y. Guo, F. Zhang, X. Gu L. Belau S. Leone M. Ahmed B. Braams J. Bowman

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