Combined ab initio and density functional study of ring chain tautomerism in benzofurazan‐1‐oxide
Combined ab initio and density functional study of ring chain tautomerism in benzofurazan‐1‐oxide
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DOI：
10.1002/(sici)1096-987x(199612)17:16
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发表时间：
1996-12
影响因子：
3
通讯作者：
G. Rauhut
中科院分区：
文献类型：
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作者：
G. Rauhut
用从头算和非局域密度泛函理论重新研究了苯并呋咱-1-氧化物（苯并氧化呋咱）的环链互变异构。在Hartree-Fock水平甚至MP2水平上，通过波函数预测该反应的能量和几何形状的失败可以通过使用Becke和Lee，Young和Parr的非局部三参数混合交换相关泛函（B3-LYP）来克服。通过邻二亚硝基苯的两种可能的反应路径已经研究，考虑基态和过渡态。在B3-LYP理论水平上，两种机制显示出非常相似的活化能，与实验结果非常一致。由自洽反应场（SCRF）模型模拟的溶剂效应会导致优选机制以及最稳定的中间体发生变化。© 1996年由John Wiley & Sons，Inc.
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. © 1996 by John Wiley & Sons, Inc.