On the dissociation of aromatic radical anions in solution.
A new theoretical formulation is given for the reaction rate and path for the important reaction class of aromatic radical anion dissociation in solution [Ar-X]-.-->Ar. + X-, and is illustrated for the case of the cyanochlorobenzene radical anion [CN-phi-CI]-. 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.
Laage
Damien
D
Département de Chimie CNRS UMR 8640 PASTEUR Ecole Normale Supérieure, 24 rue Lhomond 75231 Paris, France.
Burghardt
Irène
I
Sommerfeld
Thomas
T
Hynes
James T
JT