Abstract
We present a new dynamic continuum ansatz to describe the frictional force exerted on moving wave packets in a solvent cage. The solvent interferes on the femtosecond time scale, but decides the reaction outcome.
Highlights
Photoinduced bond cleavage in solutionMost reactions in organic as well as biochemistry take place in solution
Photoinduced bond cleavage is often employed for the generation of carbocations and radicals
EPJ Web of Conferences intersection (CoIn) coupling the homolytic and heterolytic product channel could in principle lead to a fast depletion of the radical population
Summary
Most reactions in organic as well as biochemistry take place in solution. Electrostatic solvent effects are known to change the reactivity of the solute dramatically. The same holds for photochemical reactions where often dissociative processes are included. The electrostatic influence and the dynamic impact of the solvent becomes important. Like in phosphonium salts [1], the solvent cage substantially decelerates the photogenerated fragments depending on the viscosity of the solvent. Subsequent distance dependent processes like electron or energy transfer between the photofragments become feasible as the fragments are kept at a reasonable distance. On the shorter time scale below 200 fs frictional deceleration is essential. The molecular system gets the chance to deposit energy into motions additional to the primary dissociation coordinate. Thereby regions decisive for the branching into competing product channels can be reached
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