Polymer degradation through chemical change: a quantum-based test of inferred reactions in irradiated polydimethylsiloxane.

Chemical reaction schemes are key conceptual tools for interpreting the results of experiments and simulations, but often carry implicit assumptions that remain largely unverified for complicated systems. Established schemes for chemical damage through crosslinking in irradiated silicone polymers comprised of polydimethylsiloxane (PDMS) date to the 1950's and correlate small-molecule off-gassing with specific crosslink features. In this regard, we use a somewhat reductionist model to develop a general conditional probability and correlation analysis approach that tests these types of causal connections between proposed experimental observables to reexamine this chemistry through quantum-based molecular dynamics (QMD) simulations. Analysis of the QMD simulations suggests that the established reaction schemes are qualitatively reasonable, but lack strong causal connections under a broad set of conditions that would enable making direct quantitative connections between off-gassing and crosslinking. Further assessment of the QMD data uncovers a strong (but nonideal) quantitative connection between exceptionally hard-to-measure chain scission events and the formation of silanol (Si-OH) groups. Our analysis indicates that conventional notions of radiation damage to PDMS should be further qualified and not necessarily used . In addition, our efforts enable independent quantum-based tests that can inform confidence in assumed connections between experimental observables without the burden of fully elucidating entire reaction networks.