Estimating the Complete Basis Set Extrapolation Error through Random Walks

Abstract

We propose a method for estimating the uncertainty of a result obtained through extrapolation to the complete basis set limit. The method is based on an ensemble of random walks that simulate all possible extrapolation outcomes that could have been obtained if results from larger basis sets had been available. The results assembled from a large collection of random walks can then be analyzed statistically, providing a route for uncertainty prediction at the confidence level required in a particular application. The method is free of empirical parameters and compatible with any extrapolation scheme. The proposed technique is tested in a series of numerical trials by comparing the determined confidence intervals with reliable reference data. We demonstrate that the predicted error bounds are reliable and tight yet conservative at the same time.