Automatic generation of complementary auxiliary basis sets for explicitly correlated methods

Abstract

Explicitly correlated calculations, aside from the orbital basis set, typically require three auxiliary basis sets: Coulomb-exchange fitting (JK), resolution of the identity MP2 (RI-MP2), and complementary auxiliary basis set (CABS). If unavailable for the orbital basis set and chemical elements of interest, the first two can be auto-generated on the fly using existing algorithms, but not the third. In this paper, we present a quite simple algorithm named autoCABS; a Python implementation under a free software license is offered at Github. For the cc-pVnZ-F12 (n = D,T,Q,5), the W4-08 thermochemical benchmark, and the HFREQ2014 set of harmonic frequencies, we demonstrate that autoCABS-generated CABS basis sets are comparable in quality to purpose-optimized OptRI basis sets from the literature, and that the quality difference becomes entirely negligible as n increases.

Keywords: automatic fitting basis set generation; complementary auxiliary basis set; explicitly correlated methods.