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A study of basis set effects on structures and electronic structures of phosphine oxide and fluorophosphine oxide

✍ Scribed by Andrew Streitwieser Jr.; Robert S. McDowell; Rainer Glaser

Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
523 KB
Volume
8
Category
Article
ISSN
0192-8651

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✦ Synopsis

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.

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