Selection, calibration, and validation of coarse-grained models of atomistic systems

This dissertation examines the development of coarse-grained models of atomistic systems for the purpose of predicting target quantities of interest in the presence of uncertainties. It addresses fundamental questions in computational science and engineering concerning model selection, calibration, and validation processes that are used to construct predictive reduced order models through a unified Bayesian framework. This framework, enhanced with the concepts of information theory, sensitivity analysis, and Occam's Razor, provides a systematic means of constructing coarse-grained models suitable for use in a prediction scenario. The novel application of a general framework of statistical calibration and validation to molecular systems is presented. Atomistic models, which themselves contain uncertainties, are treated as the ground truth and provide data for the Bayesian updating of model parameters. The open problem of the selection of appropriate coarse-grained models is addressed through the powerful notion of Bayesian model plausibility. A new, adaptive algorithm for model validation is presented. The Occam-Plausibility ALgorithm (OPAL), so named for its adherence to Occam's Razor and the use of Bayesian model plausibilities, identifies, among a large set of models, the simplest model that passes the Bayesian validation tests, and may therefore be used to predict chosen quantities of interest. By discarding or ignoring unnecessarily complex models, this algorithm contains the potential to reduce computational expense with the systematic process of considering subsets of models, as well as the implementation of the prediction scenario with the simplest valid model. An application to the construction of a coarse-grained system of polyethylene is given to demonstrate the implementation of molecular modeling techniques; the process of Bayesian selection, calibration, and validation of reduced-order models; and OPAL. The potential of the Bayesian framework for the process of coarse graining and of OPAL as a means of determining a computationally conservative valid model is illustrated on the polyethylene example.