Combined ab initio and density functional study of ring chain tautomerism in benzofurazan-1-oxide

by Rauhut, G.

The ring chain tautomerism of benzofurazan-1-oxide (benzofuroxan) has been reinvestigated using ab initio as well as nonlocal density functional theory. The failure in predicting energies and geometries of this reaction by wave functions at the Hartree-Fock or even at the MP2 level could be overcome by using the nonlocal three-parameter hybrid exchange correlation functional of Becke and Lee, Young, and Parr (B3-LYP). Two possible reaction paths via ortho-dinitrosobenzene have been studied, considering both ground and transition states. At the B3-LYP level of theory, both mechanisms show very similar activation energies which are in excellent agreement with experimental results. Solvent effects, simulated by a self-consistent reaction field (SCRF) model, cause alternations in the preferred mechanism as well as in the most stable intermediates.

Journal
Journal of Computational Chemistry
Volume
17
Issue
16
Year
1996
Start Page
1848-1856
URL
https://dx.doi.org/10.1002/(sici)1096-987x(199612)17:16<1848::aid-jcc5>3.0.co;2-n
ISBN/ISSN
1096-987X; 0192-8651
DOI
10.1002/(sici)1096-987x(199612)17:16<1848::aid-jcc5>3.0.co;2-n