A B3LYP and MP2(full) theoretical investigation into explosive sensitivity upon the formation of the molecule-cation interaction between the nitro group of RNO2 (R = -CH3, -NH2, -OCH3) and Na+
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鈰疦a+ < NM鈰疢g2+ < NM鈰疉l3+, NA鈰疦a+ < NA鈰疢g2+ < NA鈰疉l3+ and MN鈰疦a+ < MN鈰疢g2+, 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 (螖BDE) in comparison with the monomer correlates well with the molecule-cation interaction energy Eint., electron density 蟻BCP(O6鈰痗ation), delocalization energy and mulliken charge of the nitro group. The linear relationship between the mulliken charge of the nitro group in complex and the O6鈰痗ation distance or 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.