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Femtosecond real-time probing of reactions. I. The technique

Rosker, Mark J. and Dantus, Marcos and Zewail, Ahmed H. (1988) Femtosecond real-time probing of reactions. I. The technique. Journal of Chemical Physics, 89 (10). pp. 6113-6127. ISSN 0021-9606. doi:10.1063/1.455427.

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When a chemical bond is broken in a direct dissociationreaction, the process is so rapid that it has generally been considered instantaneous and therefore unobservable. But the fragments formed interact with one another for times on the order of 10^(−13) s after the photon has been absorbed. On this time scale the system passes through intermediate transition configurations; the totality of such configurations have been, in the recent literature, designated as "transition states." Femtosecond transition‐state spectroscopy (FTS) is a real‐time technique for probing chemical reactions. It allows the direct observation of a molecule in the process of falling apart or in the process of formation. In this paper, the first in a series on femtosecond real‐time probing of reactions, we examine the technique in detail. The concept of FTS is explored, and the interrelationship between the dynamics of chemical reactions and molecular potential energy surfaces is considered. The experimental method, which requires the generation of spectrally tunable femtosecond optical pulses, is detailed. Illustrative results from FTS experiments for several elementary reactions are presented, and we describe methods for relating these results to the potential energy surface(s).

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Additional Information:© 1988 American Institute of Physics. Received 12 July 1988; accepted 11 August 1988. This work was supported by AFOSR (Grant No. 87-0071) Contribution No. 7813. During the course of these studies and the development ofFTS, we have benefited from fruitful discussions and collaborations with Professor R. Bernstein and Professor R. Bersohn. We also had very helpful discussions with Professor R. Zare, R. Dixon, J. Simons, and K. Wilson on the alignment problem. Finally, we want to thank Dr. T. Rose of our group for helpful discussions, especially relating to his contributions to the work on alkali halides reported in Refs. 2 and 3.
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Air Force Office of Scientific Research (AFOSR)87-0071
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Arthur Amos Noyes Laboratory of Chemical Physics7813
Issue or Number:10
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Official Citation:Femtosecond real‐time probing of reactions. I. The technique Mark J. Rosker, Marcos Dantus and Ahmed H. Zewail J. Chem. Phys. 89, 6113 (1988);
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70156
Deposited By: Ruth Sustaita
Deposited On:06 Sep 2016 19:08
Last Modified:11 Nov 2021 04:25

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