A means of extrapolating from double and triple-valence basis sets to a complete basis set is examined in the context of the pnicogen bonds in the BH2P⋯NH3 complexes, with B = CH3, H, NH2, CF3, OH, Cl, F, and NO2. Binding energies converge smoothly, and the trends for the various substituents B are unaffected by the basis set size, extrapolation, or level of inclusion of electron correlation, including MP2 and CCSD(T). The approach appears to be successful also for H-bonded systems, in particular the water dimer. In the event that full extrapolation within the context of CCSD(T) is not feasible, several more economical but attractive options are suggested, including a quantitative measure of the accuracy to be expected with each.
Extrapolation to the Complete Basis Set Limit for Binding Energies of Noncovalent InteractionsComput. Theor. Chem.
Citation InformationExtrapolation to the Complete Basis Set Limit for Binding Energies of Noncovalent Interactions S. Scheiner Comput. Theor. Chem. 2012 998 9-13