An efficient extrapolation to the (T)/CBS limit

摘要

We extrapolate to the perturbative triples (T)/complete basis set (CBS) limit using double ζ basis sets without polarization functions (Wesleyan-1-Triples-2ζ or "Wes1T-2Z") and triple ζ basis sets with a single level of polarization functions (Wesleyan-1-Triples-3ζ or "Wes1T-3Z"). These basis sets were optimized for 102 species representing the first two rows of the Periodic Table. The species include the entire set of neutral atoms, positive and negative atomic ions, as well as several homonuclear diatomic molecules, hydrides, rare gas dimers, polar molecules, such as oxides and fluorides, and a few transition states. The extrapolatedWes1T-(2,3)Z triples energies agree with (T)/CBS benchmarks to within ±0.65 mE_h, while the rms deviations of comparable model chemistries W1, CBS-APNO, and CBS-QB3 for the same test set are ±0.23 mE_h, ±2.37 mE_h, and ±5.80 mE_h, respectively. The Wes1T-(2,3)Z triples calculation time for the largest hydrocarbon in the G2/97 test set, C_6H_5Me~+, is reduced by a factor of 25 when compared to W1. The cost-effectiveness of the Wes1T-(2,3)Z extrapolation validates the usefulness of the Wes1T-2Z and Wes1T-3Z basis sets which are now available for a more efficient extrapolation of the (T) component of any composite model chemistry.