A B3LYP and MP2(full) theoretical investigation into explosive sensitivity upon the formation of the molecule-cation interaction between the nitro group of 3,4-dinitropyrazole and H+, Li+, Na+, Be2+ or Mg2+

作者：Du, Shan; Wang, Yong; Chen, Li-zhen; Shi, Wen-jing; Ren, Fu-de^*; Li, Yong-xiang; Wang, Jian-long; Cao, Duan-lin

来源：Journal of Molecular Modeling, 2012, 18(5): 2105-2115.

DOI：10.1007/s00894-011-1229-7

• 3,4-dinitropyrazole
• Molecule-cation interaction
• MP2
• Sensitivity
• Trigger bond

The explosive sensitivity upon the formation of molecule-cation interaction between the nitro group of 3,4-dinitropyrazole (DNP) and H+, Li+, Na+, Be2+ or Mg2+ has been investigated using the B3LYP and MP2(full) methods with the 6-311++G** and 6-311++G(2df,2p) basis sets. The bond dissociation energy (BDE) of the C3-N7 trigger bond has also been discussed for the DNP monomer and the corresponding complex. The interaction between the oxygen atom of nitro group and H+ in DNPaEuro broken vertical bar H+ is partly covalent in nature. The molecule-cation interaction and bond dissociation energy of the C3-N7 trigger bond follow the order of DNPaEuro broken vertical bar Be2+ > DNPaEuro broken vertical bar Mg2+ > DNPaEuro broken vertical bar Li+ > DNPaEuro broken vertical bar Na+. Except for DNPaEuro broken vertical bar H+, the increment of the trigger bond dissociation energy in comparison with the DNP monomer correlates well with the molecule-cation interaction energy, natural charge of the nitro group, electron density rho (BCP(C3-N7)), delocalization energy E ((2)) and NBO charge transfer. The analyses of atoms in molecules (AIM), natural bond orbital (NBO) and electron density shifts have shown that the electron density of the nitro group shifts toward the C3-N7 trigger bond upon the formation of the molecule-cation interaction. Thus, the trigger bond is strengthened and the sensitivity of DNP is reduced.

• 出版日期2012-5
• 单位山西医科大学; 中北大学