Modified chemistry of siloxanes under tensile stress: interaction with environment.

We present first principles molecular dynamics simulations of stretched siloxane oligomers in an environment representative of that present in single molecule atomic force microscopy experiments. We determine that the solvent used (hexamethyldisiloxane) does not influence the stretching of the siloxane in the high force regime or the rupture process, but trace amounts of water can induce rupture before the maximum siloxane extension has been attained. This would result in a significantly lower rupture force. The simulations show that the rupture of a covalent bond through a reaction with a molecule from the environment, which would not normally occur between the species when the polymer is not stressed, is possible, opening a route to mechanically induced chemical reactions. The attack of the normally hydrophobic siloxane by water when it is stretched has wider implications for the material failure under tensile stress, where trace amounts of water could induce tearing of the material.