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A study of basis set effects on structures and electronic structures of phosphine oxide and fluorophosphine oxide
Author(s) -
Streitwieser Andrew,
McDowell Robert S.,
Glaser Rainer
Publication year - 1987
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540080606
Subject(s) - phosphine oxide , atomic orbital , basis set , basis (linear algebra) , electronic structure , oxide , chemistry , representation (politics) , computational chemistry , phosphine , electron , molecular physics , mathematics , physics , geometry , quantum mechanics , density functional theory , organic chemistry , politics , political science , law , catalysis
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 2 sp 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 H 3 P + 0 − , rather than H 3 P0.