Extrapolation to the Complete Basis Set Limit for Binding Energies of Noncovalent Interactions
Comput. Theor. Chem.
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 Interactions S. Scheiner Comput. Theor. Chem. 2012 998 9-13