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Femtosecond real-time probing of reactions. III. Inversion to the potential from femtosecond transition-state spectroscopy experiments

Bernstein, Richard B. and Zewail, Ahmed H. (1989) Femtosecond real-time probing of reactions. III. Inversion to the potential from femtosecond transition-state spectroscopy experiments. Journal of Chemical Physics, 90 (2). pp. 8295-842. ISSN 0021-9606. doi:10.1063/1.456108.

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Femtosecond transition-state spectroscopy (FTS) of elementary reactions [M. Dantus, M. J. Rosker, and A. H. Zewail, J. Chem. Phys. 87, 2395 (1987)] provides real-time observations of photofragments in the process of formation. A classical mechanical description of the time-dependent absorption of fragments during photodissociation [R. Bersohn and A. H. Zewail, Ber. Bunsenges. Phys. Chem. 92, 373 (1988)] forms the basis for the present scheme for relating observations to the potential energy surface. A direct inversion scheme is presented that allows the difference in the two relevant excited-state potential curves to be deduced from observed transients at different probe wavelength tunings. In addition, from the shape and dependence of the transients on pump wavelength, information on the lower of the two potential curves (i.e., that of the dissociating molecule) is obtained. The methodology is applied to the experimental FTS data (Dantus et al.) on the CN photofragment from the ICN photodissociation.

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Additional Information:© 1989 American Institute of Physics. Received 23 August 1988; accepted 1 October 1988. This work was supported by grants to A.H.Z. and to R.B.B. from the National Science Foundation and to A.H.Z. from the Air Force Office of Scientific Research. This paper is the result of enjoyable collaboration and "administration-free" time when R.B.B. Sherman Fairchild Distinguished Scholar at Caltech and A.H.Z. was a Guggenheim Fellow at UCLA. Without this opportunity, which allowed us to focus on the research and to enjoy many hours of discussion, the story told here would not have been possible. Finally, we wish to thank Mr. R. Scott Mackay of UCLA for the calculations and plots of Figs. 7, 11, and 12. [A.H.Z. was a] John Simon Guggenheim Foundation Fellow. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 780.
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John Simon Guggenheim FoundationUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Sherman Fairchild FoundationUNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics7808
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