Dynamics of Molecules near Ionization
Abstract
In this paper, we report our experimental studies, using femtosecond-resolved mass spectrometry, and theoretical calculations of the potential energy surfaces, using density functional theory, for 10 aliphatic amines (substituted ammonia) excited directly near the ionization continuum. By probing parent and fragment masses, we are able to decipher pathways of the reactive α-cleavage and the nonreactive internal conversion, a precursor for the following chemistry. The bifurcation in these channels is related to the structure, as evidenced by the dramatic effect of α-substitution vs N-substitution on the time scale of the dynamics-femtosecond vs picosecond rates. For all molecules studied, the observed branching is dependent on the change of character of the state, ionic and/or neutral, along the reaction coordinate, and this change blurs the distinction between Rydberg and Superexcited states in their subsequent reactivity.
Additional Information
© 2003 American Chemical Society. Received: June 30, 2003; In Final Form: September 22, 2003, Publication Date (Web): November 21, 2003. This work was supported by the U.S. Office of Naval Research and the U.S. Air Force Office of Scientific Research. C.K., a Feodor Lynen Fellow from the Alexander von Humboldt Foundation, acknowledges the foundation and Caltech for support. T.I.S. was supported by Statens Naturvidenskabelige Forskningsraad, the Denmark-America foundation, and by Caltech, and thanks Dr. Steen Hammerum, University of Copenhagen, for valuable discussions.Additional details
- Eprint ID
- 69714
- Resolver ID
- CaltechAUTHORS:20160817-132621821
- Office of Naval Research (ONR)
- Air Force Office of Scientific Research (AFOSR)
- Alexander von Humboldt Foundation
- Statens naturvidenskabelige Forskningsraad
- Denmark-America Foundation
- Caltech
- Created
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2016-08-17Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field