Substituent effects in second‐row molecules: Basis set performance in calculations of normal valency phosphorus and sulfur compounds

Abstract

AbstractAb inito molecular orbital calculations of the phosphorus‐ and sulfur‐containing series PH2X, PH3X+, SHX, and SH2X+ (X = H, CH3, NH2, OH, F) have been carried out over a range of Gaussian basis sets and the results (optimized geometrical structures, relative energies, and electron distributions) critically compared. As in first‐row molecules there are large discrepancies between substituent interaction energies at different basis set levels, particularly in electron‐rich molecules; use of basis sets lower than the supplemented 6‐31G basis incurs the risk of obtaining substituent stabilizations with large errors, including the wrong sign. Only a small part of the discrepancies is accounted for by structural differences between the optimized geometries. Supplementation of low level basis sets by d functions frequently leads to exaggerated stabilization energies for π‐donor substituents. Poor performance also results from the use of split valence basis sets in which the valence shell electron density is too heavily concentrated in diffuse component of the valence shell functions, again likely to occur in electron‐rich molecules. Isodesmic reaction energies are much less sensitive to basis set variation, but d function supplementation is necessary to achieve reliable results, suggesting a marginal valence role for d functions, not merely polarization of the bonding density. Optimized molecular geometries are relatively insensitive to basis set and electron population analysis data, for better‐than‐minimal bases, are uniform to an unexpected degree.