Premium
Variational biorthogonal valence bond descriptions of 1,3‐dipoles
Author(s) -
Malcolm Nathaniel O. J.,
McDouall Joseph J. W.
Publication year - 1994
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.540151206
Subject(s) - biorthogonal system , modern valence bond theory , generalized valence bond , valence bond theory , valence (chemistry) , chemistry , orbital hybridisation , atomic orbital , dipole , atomic physics , computational chemistry , electron , physics , quantum mechanics , computer science , wavelet transform , organic chemistry , wavelet , artificial intelligence
The variational biorthogonal valence bond method is applied to the π‐electrons of six 1,3‐dipoles (CH 2 N 2 , HCNO, CH 2 NHO, N 2 O, O 3 , NO 2 ). The results are compared with those from other valence bond techniques, including a detailed comparison with the spin‐coupled valence bond approach. For CH 2 N 2 , HCNO, CH 2 NHO, and N 2 O, zwitterionic structures are predicted and it is shown that the variational biorthogonal valence bond method leads to orbitals and configuration weights which are essentially indistinguishable from those of the spin‐coupled valence bond method. However, for O 3 and NO 2 the techniques give contradictory results. The biorthogonal valence method predicts O 3 and NO 2 to be spin‐paired diradicals. Evidence from other calculations on O 3 is discussed. © 1994 by John Wiley & Sons, Inc.