Stress-dependent molecular pathways of silica–water reaction

Stress-corrosion of silica by water is studied by exploring the stress-dependent potential energy surface computed quantum mechanically at the level of molecular orbital theory. An ordered silica nanorod with clearly defined nominal tensile stress is constructed to model a structural unit of the stressed crack tip. Three competing hydrolysis reaction pathways are determined, each involving a distinct initiation step. Water dissociation, molecular chemisorption, and direct siloxane bond rupture dominate at low, intermediate, and high stress levels, respectively. A linear stress dependence in the thermodynamic driving force, not commonly considered in the criterion of brittle fracture initiation, is shown to originate from surface relaxation associated with bond rupture. This effect is particularly important in determining the Griffith condition of crack extension for nano-sized systems when spatial accommodation of foreign molecules is involved in the process of bond breaking. The physical see front matter r 2005 Elsevier Ltd. All rights reserved. .jmps.2005.02.002 nding author. Tel.: +1617 253 3809; fax: +1 617 258 8863. dress: [email protected] (S. Yip).