Py. Cheng et al., MICROSCOPIC SOLVATION AND FEMTOCHEMISTRY OF CHARGE-TRANSFER REACTIONS- THE PROBLEM OF BENZENE(S)-IODINE BINARY COMPLEXES AND THEIR SOLVENTSTRUCTURES, Chemical physics letters, 242(4-5), 1995, pp. 369-379
Charge-transfer reactions are studied on the femtosecond and picosecon
d time scales and under controlled composition in a molecular beam. Th
e system of interest is iodine in aromatic and non-aromatic solvents,
which goes back to Hildebrand and Mulliken almost 50 years ago. For th
e first time, the isolated binary complex and its solvated structural
dynamics are studied. The product iodine atoms are positively identifi
ed and the concept of harpoon mechanism introduced. The dynamics are r
elated to the impact geometry of the transition state and the electron
ic structure. A global potential energy surface is described with mole
cular dynamics detailing the motion in the reaction coordinates.