The Role of Solute/Solvent Electronic Interaction in the Femtosecond Dynamics of the Bromide/Benzene Cation Contact Ion Pair in Benzene Solution

The bromide/benzene cation contact ion pair was prepared in benzene solution by ultrafast excitation of the bromine atom/benzene molecule charge transfer complex. Bromine atoms were prepared in situ by photolysis of [alpha]-bromoacetophenone. A simple first-order charge recombination reaction was ob...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1994-09, Vol.98 (37), p.9102-9105
Main Authors: Jarzeba, Wlodzimierz, Schlief, Ralph E, Barbara, Paul F
Format: Article
Language:English
Subjects:
400102 > Chemical & Spectral Procedures
400500 > Photochemistry
ABSORPTION SPECTROSCOPY
AROMATICS
BENZENE
BROMIDES
BROMINE COMPOUNDS
CHEMICAL REACTIONS
COMPILED DATA
DATA
DECOMPOSITION
DIMERIZATION
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
GROUND STATES
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ION PAIRS
KINETICS
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
POLYMERIZATION
REACTION KINETICS
RECOMBINATION
SPECTROSCOPY 400201 > Chemical & Physicochemical Properties
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Description
Summary:The bromide/benzene cation contact ion pair was prepared in benzene solution by ultrafast excitation of the bromine atom/benzene molecule charge transfer complex. Bromine atoms were prepared in situ by photolysis of [alpha]-bromoacetophenone. A simple first-order charge recombination reaction was observed to be the only significant decay process for the ion pair. Despite the apparent simplicity of the charge recombination kinetics, spectroscopic data show that the reaction involves a rapidly formed benzene dimer cation. Various issues of the dynamics involving the dimer cation and the ion pair have been investigated. 17 refs., 3 figs., 1 tab.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100088a002