Femtodynamics Reflected in Nanoseconds: Bimolecular Free Electron Transfer in Nonpolar Media

Abstract

The (free) electron transfer (FET) from electron donor molecules to parent solvent radical cations of alkanes and alkyl chlorides exhibits mechanistic peculiarities that are conditioned by the low polarity of these solvents. Because of the negligible solvation of ions in such systems and the almost complete lack of an activation barrier, the electron jump takes place at the very first encounter of the reactants and, as such, in extremely short times of <or=10(-15) s. Molecular oscillations (deformation, bending) occurring within the femtosecond time domain result directly in significant changes of the pi- or n-electron distribution in the HOMO ground state of the donor molecule, thereby generating a distribution of conformers. This is considered to be a rationale for a possible generation of different product radical cations in the free electron transfer, which exhibit different spin and charge distribution and, consequently different stability. Experimentally, the latter has been verified for aromatic donors, substituted with mobile, i.e., not rigidly fixed heteroatom-centered groups (various phenol type compounds, thiophenols, aromatic amines, benzyltrimethylsilanes etc.). The individually characteristic product distribution could be visualized and quantified by time-resolved spectroscopy in the nanosecond time domain. On the basis of a manifold of experimental data and supported by quantum-chemical calculations, the free electron transfer phenomenon is analyzed and discussed in detail in this summarizing report. The results presented here stand also for a, seemingly paradox, situation in which the products of a diffusion-controlled bimolecular reaction are governed by femtosecond events.