Microscopic solvation and femtochemistry of charge-transfer reactions: the problem of benzene(s)-iodine binary complexes and their solvent structures

Charge-transfer reactions are studied on the femtosecond and picosecond time scales and under controlled composition in a molecular beam. The system of interest is iodine in aromatic and non-aromatic solvents, which goes back to Hildebrand and Mulliken almost 50 years ago. For the first time, the isolated binary complex and its solvated structural dynamics are studied. The product iodine atoms are positively identified and the concept of harpoon mechanism introduced. The dynamics are related to the impact geometry of the transition state and the electronic structure. A global potential energy surface is described with molecular dynamics detailing the motion in the reaction coordinates.