THE IDENTITY OF THE 6 NITROGEN-ATOMS (N-6) SPECIES

被引:37
作者
HA, TK [1 ]
NGUYEN, MT [1 ]
机构
[1] UNIV LOUVAIN,DEPT CHEM,B-3001 LOUVAIN,BELGIUM
关键词
D O I
10.1016/0009-2614(92)86132-2
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Structures of six nitrogen atom species (N6) have been reconsidered using high-level ab initio calculations. Harmonic vibrational wavenumbers obtained at the MP2/6-31G (d) level show that both the benzene analogue (hexazine, D6h) and the transbent open-chain (C2h) structures are not energy minima as previously reported, but rather transition structures on the N6 potential energy surface. The corresponding equilibrium structures are a cyclic complex of the two azide radicals and a C2 open chain, respectively. The open-chain form lies lower in energy than the cylic isomer (almost-equal-to 11 kcal/mol at the MP4/6-311 + G(d) + ZPE). Calculated vertical excitation energies also suggest that the open-chain diazide (N3)2 is the best candidate for the species exhibiting a yellow color (lambda(max) = 380 nm) observed by Vogler, Wright and Kunkley in their flash photoloytic experiment.
引用
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页码:179 / 183
页数:5
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