A Study of Basis Set Effects on Structures and Electronic Structures of Phosphine Oxide and Fluorophosphine Oxide
A variety of basis sets have been used for geometric and electronic structure studies. Electronic effects were measured using integrated spatial electron populations (ISEP). The two largest basis sets used, 6-31G* and DZ+P, give significantly different results. Use of two d-orbital sets (6-31G*[dd]) or decontraction of the 2sp shell on phosphorus has little further effect. d-Orbitals on oxygen are required for consistent electronic structure results, and d-orbitals on fluorine have a small but significant effect. Use of diffuse functions, required for anions, is not recommended with small basis sets on neutral molecules. Large negative charges (≈-1.5) on oxygen are given by all of the larger basis sets by the ISEP procedure and indicate that the PO bond in these compounds is largely semi-polar. The best simple symbolic representation of phosphine oxide is H3P+—0-, rather than H3P+═0.
A. J. Streitwieser et al., "A Study of Basis Set Effects on Structures and Electronic Structures of Phosphine Oxide and Fluorophosphine Oxide," Journal of Computational Chemistry, vol. 8, no. 6, pp. 788-793, Wiley-Blackwell, Sep 1987.
The definitive version is available at https://doi.org/10.1002/jcc.540080606
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