科研之友
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摘要
The changes of the bond dissociation energy of the trigger bond (C-NO2, N-NO2 or O-NO2) and nitro group charge upon the formation of the molecule-cation interaction between the nitro group of RNO2 (R = -CH3, -NH2, -OCH3) and cation (Na+, Mg2+, Al3+) have been systematically investigated using the B3LYP and MP2(full) methods with the 6-311++G**, 6-311++G(2d,p) and aug-cc-pVTZ basis sets. The trigger bond dissociation energy is the order of NM center dot center dot center dot Na+ < NM center dot center dot center dot Mg2+ < NM center dot center dot center dot Al3+, NA center dot center dot center dot Na+ < NA center dot center dot center dot Mg2+ < NA center dot center dot center dot Al3+ and MN center dot center dot center dot Na+ < MN center dot center dot center dot Mg2+, respectively. The strength of the trigger bond is enhanced and the explosive sensitivity is reduced upon the formation of molecule-cation interaction. The increment of the trigger bond dissociation energy (Delta BDE) in comparison with the monomer correlates well with the moleculecation interaction energy E-int, electron density rho(BCP(O6 center dot center dot center dot cation)). delocalization energy E-LP(O6(s))-LP(cation)((2)) and mulliken charge of the nitro group. The linear relationship between the mulliken charge of the nitro group in complex and the O6 center dot center dot center dot cation distance or E-LP(O6(d))-LP(cation)((2)) is also found. The analyzes of AIM, NBO and electron density shifts show that the electron density shifts toward the trigger bond upon the formation of the molecule-cation interaction. Thus, the trigger bond is strengthened and the sensitivity is reduced.
