Preparation of cationic intermediates by dissociative photoionization of van der Waals complexes. C/sub 6/H/sub 6/Cl/sup +/ from a C/sub 6/H/sub 6/ + HCl mixture

Journal Article · Thu May 21 00:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100295a023· OSTI ID:6365714

Walters, E A; Grover, J R; White, M G; Hui, E T

The ion (C/sub 6/H/sub 6/Cl)/sup +/ (1) has been observed as a product of dissociative photoionization of a C/sub 6/H/sub 6/ + HCl van der Walls complex. It was shown that 1 does not come from the dimer C/sub 6/H/sub 6/ x HCl but from trimers or larger clusters, most likely (C/sub 6/H/sub 6/)/sub 2/HCl. Experiments with C/sub 6/D/sup 6/ + HCl mixtures demonstrate that the departing hydrogen initially belonged to the HCl partner of the complex. The energetics and isotope studies are consistent with an ipso structure for C/sup 6/H/sup 6/Cl/sup +/, i.e., a Wheland sigma-complex. The overall process of dissociative photoionization does not have an accessible reaction channel leading to C/sub 6/H/sub 6/Cl..mu.. unless at least one solvent molecule is present. Mechanisms by which the transformation may occur are discussed.

• Research Organization: Brookhaven National Lab., Upton, NY
• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6365714
• Journal Information: J. Phys. Chem.; (United States), Vol. 91:11
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZENE
CHEMICAL REACTIONS
PHOTOIONIZATION
CHLORINE COMPLEXES
DEUTERIUM COMPOUNDS
HYDROCHLORIC ACID
DIMERS
EXPERIMENTAL DATA
MASS SPECTROSCOPY
NOZZLES
AROMATICS
COMPLEXES
DATA
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
IONIZATION
NUMERICAL DATA
ORGANIC COMPOUNDS
SPECTROSCOPY
400500* - Photochemistry