Complete Basis Set Extrapolation of Electronic Correlation Energies Using the Riemann Zeta Function.

In this article, we demonstrate the effectiveness of the method of complete basis set (CBS) extrapolation of correlation energies based on the application of the Riemann zeta function. Instead of fitting the results obtained with a systematic sequence of one-electron bases with a certain functional form, an analytic resummation of the missing contributions coming from higher angular momenta, l, is performed. The assumption that these contributions vanish asymptotically as an inverse power of l leads to an expression for the CBS limit given in terms of the zeta function. This result is turned into an extrapolation method that is very easy to use and requires no "empirical" parameters to be optimized. The performance of the method is assessed by comparing the results with very accurate reference data obtained with explicitly correlated theories and with results obtained with standard extrapolation schemes. On average, the errors of the zeta-function extrapolation are several times smaller compared with the conventional schemes employing the same sequence of bases. A recipe for the estimation of the residual extrapolation error is also proposed.