Computer-based first-principles kinetic Monte Carlo simulation of polyethylene glycol degradation in aqueous phase...

We have developed a computer-based first-principles kinetic Monte Carlo (CF-KMC) model to predict degradation mechanisms and fates of intermediates and byproducts produced from the degradation of polyethylene glycol (PEG) in the presence of hydrogen peroxide (UV/H2O2). The CF-KMC model is composed of a reaction pathway generator, a reaction rate constant estimator, and a KMC solver. The KMC solver is able to solve the predicted pathways successfully without solving ordinary differential equations. The predicted time-dependent profiles of averaged molecular weight, and polydispersitivity index (i.e., the ratio of the weight-averaged molecular weight to the number-averaged molecular weight) for the PEG degradation were validated with experimental observations. These predictions are consistent with the experimental data. The model provided detailed and quantitative insights into the time evolutions of molecular weight distribution and concentration profiles of low molecular weight products and functional groups. Our approach may be useful to predict the fates of degradation products for a wide range of complicated organic contaminants.