Basis set extrapolation in pair natural orbital theories.

Abstract

We present the results of a benchmark study of the effect of Pair Natural Orbital (PNO) truncation errors on the performance of basis set extrapolation. We find that reliable conclusions from the application of Helgaker's extrapolation method are only obtained when using tight PNO thresholds of at least 10-7. The use of looser thresholds introduces a significant risk of observing a false basis set convergence and underestimating the residual basis set errors. We propose an alternative extrapolation approach based on the PNO truncation level that only requires a single basis set and show that it is a viable alternative to hierarchical basis set extrapolation methods.