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The data suggest that, despite their approximate nature, BP free energy estimates are highly accurate – indeed they never fall outside confidence intervals from unbiased estimators for the systems where independent results could be obtained. The present study reports on (i) comparison of the approximate BP results with estimates from unbiased estimators based on the Amber99SB forcefield (ii) investigation of the effects of varying library size on BP predictions and (iii) a theoretical discussion of discretization effects which can arise in BP calculations. We examine the application of loopy BP to a number of peptides as well as the binding site of the T4 lysozyme L99A mutant. We use a “loopy BP” algorithm, which can be seen as an approximate generalization of the transfer-matrix approach to highly connected (i.e., loopy) graphs, and has previously been applied to protein calculations. 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