Zhong, Dongping and Zewail, Ahmed H. (1999) Femtosecond dynamics of dative bonding: Concepts of reversible and dissociative electron transfer reactions. Proceedings of the National Academy of Sciences of the United States of America, 96 (6). pp. 2602-2607. ISSN 0027-8424. PMCID PMC15814. http://resolver.caltech.edu/CaltechAUTHORS:ZHOpnas99
- Published Version
See Usage Policy.
Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:ZHOpnas99
With fs time, speed, and angular resolution of the elementary steps in electron transfer reactions, we report direct observation of reversible and dissociative processes for dative bonding involving covalent and ionic characters. For bimolecular reactions of various donors and acceptors we find strong correlation between the structure and the dynamics. The dynamics from the transition state to final products involve two elementary processes, with different reaction times, speed, and angular distributions. For example, for the R2S·I2 (R = C2H5) system, it is shown that after charge separation, the reversible electron transfer occurs in less than 150 fs (fastest trajectory) and is followed by the rupture of the I---I bond with the release of the first I-atom in 510 fs. However, the second process of the remaining and trapped I-atom takes 1.15 ps with its speed (500 m/s) being much smaller than the first one (1,030 m/s). The S---I---I average angle is 130°. These findings, on this and the other systems reported here, elucidate the mechanism and address some concepts of nonconcertedness, caging, and restricted energy redistribution.
|Additional Information:||© 1999, The National Academy of Sciences. Contributed by Ahmed H. Zewail, January 13, 1999. We thank Dr. Thorsten M. Bernhardt for his help and discussion. This work is supported by a grant from the National Science Foundation, the Air Force Office of Scientific Research, and the Office of Naval Research.|
|PubMed Central ID:||PMC15814|
|Official Citation:||Dongping Zhong and Ahmed H. Zewail Femtosecond dynamics of dative bonding: Concepts of reversible and dissociative electron transfer reactions PNAS 1999 96 (6) 2602-2607; doi:10.1073/pnas.96.6.2602|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Archive Administrator|
|Deposited On:||11 Jul 2005|
|Last Modified:||15 Aug 2016 18:30|
Repository Staff Only: item control page