Breaking Bonds by Mechanical Stress:  When Do Electrons Decide for the Other Side?

Using first-principles molecular dynamics, we have simulated reactions that can be induced by mechanical stress in a polymer. We have stretched a small piece of poly(ethylene glycol) (PEG) in water at finite temperature. Both the molecule and the solvent were described quantum mechanically on an equal level. The formation of ions was observed, which corresponds to a heterolytic bond cleavage. We were able to monitor the motion of the electrons during the reactions. Our simulations show that the electron transfer and the breaking of the bond occur almost simultaneously and that both processes are initiated by the approach of a solvent molecule toward the destabilized bond.