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On the Dissociation of Aromatic Radical Anions in Solution
Author(s) -
Laage Damien,
Burghardt Irène,
Sommerfeld Thomas,
Hynes James T.
Publication year - 2003
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200390009
Subject(s) - conical intersection , chemistry , dissociation (chemistry) , ion , photochemistry , ground state , radical ion , reaction rate , computational chemistry , reaction mechanism , dimethylformamide , molecule , organic chemistry , solvent , atomic physics , physics , catalysis
A new theoretical formulation is given for the reaction rate and path for the important reaction class of aromatic radical anion dissociation in solution [ArX] − . →Ar . +X − , and is illustrated for the case of the cyanochlorobenzene radical anion [CNΦCl] − . in dimethylformamide. Among the theory's novel features is the inclusion of the conical intersection aspect of this ground electronic state problem, which is key in allowing the reaction to occur and which has a significant impact on the reaction barrier height. Reasonable agreement with the experimental rate is found.