Ultrafast Reaction Dynamics

MAY 01, 1990

With new laser techniques and with gas phase and molecular beam experiments, it is now possible to determine the ultrafast motion in isolated chemical reactions—chemistry on the 10⁻¹³‐second time scale.

DOI: 10.1063/1.881233

Martin Gruebele

Ahmed H. Zewail

A decade ago this magazine devoted a special issue to laser chemistry (see PHYSICS TODAY, November 1980). One of the articles emphasized the importance of time scales in chemical reactions and the possible use of ultrashort lasser pulses to induce chemistry. Over the past 10 years new laser techniques, and gas‐phase and molecular‐beam experiments, have revealed much about the fundamental steps of elementary chemical reactions. These approaches and the tremendous detail they have exposed about the dynamics of chemical reactions are the subject of the present article.

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References

1. A. H. Zewail, R. B. Bernstein, Chem. Eng. News 66, 24 (1988), and references therein.https://doi.org/CENEAR
2. H. W. Cruse, P. J. Dagdigian, R. N. Zare, Faraday Disc. Chem. Soc. 55, 277 (1973).
3. J. C. Polanyi, Angew. Chem. Int. Ed. Engl. 26, 952 (1987).https://doi.org/ACIEAY
4. D. R. Hershbach, Angew. Chem. Int. Ed. Engl. 26, 1221 (1987). https://doi.org/ACIEAY
Y. T. Lee, Angew. Chem. Int. Ed. Engl. 26, 939 (1987).https://doi.org/ACIEAY
5. R. B. Bernstein, S. E. Choi, S. Stolte, J. Chem. Soc., Faraday Trans. 2 85, 1097 (1989).
6. C. H. Greene, R. N. Zare, Annu. Rev. Phys. Chem. 33, 119 (1982). https://doi.org/ARPLAP
R. Bersohn, J. Phys. Chem. 88, 5145 (1984). https://doi.org/JPCHAX
M. Brouard, M. T. Martinez, C. J. Milne, J. P. Simons, J. X. Wang, Chem. Phys. Lett. 165, 423 (1990). https://doi.org/CHPLBC
G. E. Hall, P. L. Houston, Annu. Rev. Phys. Chem. 40, 375 (1989).https://doi.org/ARPLAP
7. R. D. Levine, R. B. Bernstein, Molecular Reaction Dynamics and Chemical Reactivity, Oxford U.P., New York (1987).
8. For further discussion of product‐state distributions, see I.‐C. Chen, W. H. GreenJr, C. B. Moore, J. Chem. Phys. 89, 314 (1988).https://doi.org/JCPSA6
For further discussion of state‐to‐state reaction rates, see E. D. Potter, M. Gruebele, L. Khundkar, A. H. Zewail, Chem. Phys. Lett. 164, 463 (1989).https://doi.org/CHPLBC
9. For more on experiment, see the work of F. Crim, R. Huber, S. Leone, H. Reisler and C. Wittig, reviewed in ref 1. For more on theory, see the work of K. Freed, R. Marcus, W. Miller, M. Quack, R. Schinke, M. Shapiro, J. Troe and others, reviewed in ref. 1.
10. H.‐J. Foth, J. C. Polanyi, H. H. Telle, J. Phys. Chem. 86, 5027 (1982).
11. T. C. Maguire, P. R. Brooks, R. F. Curl, J. H. Spence, S. Ulvick, J. Chem. Phys. 85, 844 (1986).https://doi.org/JPCHAX
12. J.‐C. Nieh, J. Valentini, Phys. Rev. Lett. 60, 519 (1988).https://doi.org/PRLTAO
13. R. B. Metz, A. Weaver, S. E. Bradforth, T. N. Kitsopoulos, D. M. Neumark, J. Phys. Chem. 94, 1377 (1990).https://doi.org/JPCHAX
14. W. Kaiser, ed., Ultrashort Laser Pulses, Topics in Applied Physics 60, Springer‐Verlag, New York (1988), and references therein. S. L. Shapiro, ed., Ultrashort Light Pulses, Topics in Applied Physics 18, Springer‐Verlag, New York (1977).
15. C. V. Shank, Science 233, 1276 (1986), and references therein.https://doi.org/SCIEAS
16. A. H. Zewail, Science 242, 1645 (1988), and references therein.
L. Khundkar, A. H. Zewail, Annu. Rev. Phys. Chem. 41 (1990), in press.https://doi.org/SCIEAS
17. I. W. M. Smith, Nature 343, 691 (1990).https://doi.org/NATUAS
18. M. Dantus, R. Bowman, A. H. Zewail, Nature 343, 737 (1990). https://doi.org/NATUAS
M. Gruebele, G. Roberts, M. Dantus, R. M. Bowman, A. H. Zewail, Chem. Phys. Lett. 166, 459 (1990).https://doi.org/CHPLBC
19. J. H. Glownia, J. A. Misewich, P. P. Sorokin, J. Chem. Phys. 92, 3335 (1990).https://doi.org/JCPSA6
20. N. F. Scherer, L. R. Khundkar, R. B. Bernstein, A. H. Zewail, J. Chem. Phys. 87, 1451 (1987). https://doi.org/JCPSA6
N. F. Scherer, C. Sipes, R. B. Bernstein, A. H. Zewail, J. Chem. Phys. 92, 5239 (1990).https://doi.org/JCPSA6
21. S. Buelow, G. Radhakrishnan, J. Catanzarite, C. Wittig, J. Chem. Phys. 83, 444 (1985). https://doi.org/JCPSA6
C. Jouvet, B. Soep, J. Chem. Phys. 80, 2229 (1984).https://doi.org/JCPSA6
22. T. Baumert, B. Buehler, R. Thalweiser, G. Gerber, Phys. Rev. Lett. 64, 733 (1990).https://doi.org/PRLTAO
23. For more on experiment, see the work of R. Bersohn, R. Gentry, Y. T. Lee, P. Toennies, J. Valentini and R. N. Zare, reviewed in ref. 1. For more on potential energy surfaces, see the work of C. Horowitz, B. Liu, P. Siegbahn, D. Truhlar, reviewed in ref. 1. For more on theory, see the work of D. Kouri, A. Kuppermann, J. Light, H. Mayne, W. Miller, D. Truhlar, R. Wyatt and others, reviewed in ref. 1.
24. E. J. Heller, Acc. Chem. Res. 14, 368 (1981). https://doi.org/ACHRE4
R. Kosloff, S. A. Rice, D. J. Tannor, Chem. Phys. 139, 201 (1989).https://doi.org/CMPHC2

More about the Authors

Martin Gruebele. California Institute of Technology.

Ahmed H. Zewail. California Institute of Technology.