The relative entropy is fundamental to multiscale and inverse thermodynamic problems

We show that the relative entropy, S(rel) identical with Sigma(p(T)) ln(p(T)/p(M)), provides a fundamental and unifying framework for multiscale analysis and for inverse molecular-thermodynamic problems involving optimization of a model system (M) to reproduce the properties of a target one (T). We...

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Bibliographic Details
Published inThe Journal of chemical physics Vol. 129; no. 14; p. 144108
Main Author Shell, M Scott
Format Journal Article
LanguageEnglish
Published United States 14.10.2008
Subjects
Algorithms
Diffusion
Entropy
Kinetics
Likelihood Functions
Models, Chemical
Water - chemistry
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Summary:We show that the relative entropy, S(rel) identical with Sigma(p(T)) ln(p(T)/p(M)), provides a fundamental and unifying framework for multiscale analysis and for inverse molecular-thermodynamic problems involving optimization of a model system (M) to reproduce the properties of a target one (T). We demonstrate that the relative entropy serves as a generating function for principles in variational mean-field theory and uniqueness and gives intuitive results for simple case scenarios in model development. Moreover, we suggest that the relative entropy provides a rigorous framework for multiscale simulations and offers new numerical techniques for linking models at different scales. Finally, we show that S(rel) carries physical significance by using it to quantify the deviations of a three-site model of water from simple liquids, finding that the relative entropy, a thermodynamic concept, even predicts water's kinetic anomalies.
ISSN:1089-7690
DOI:10.1063/1.2992060