title: 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+.
abstract: The explosive sensitivity upon the formation of molecule-cation interaction between the nitro group of 3,4-dinitropyrazole (DNP) and H(+), Li(+), Na(+), Be(2+) or Mg(2+) 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 DNP…H(+) is partly covalent in nature. The molecule-cation interaction and bond dissociation energy of the C3-N7 trigger bond follow the order of DNP…Be(2+) > DNP…Mg(2+) > DNP…Li(+) > DNP…Na(+). Except for DNP…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 ρ(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.
authors: College of Chemical Engineering and Environment, North University of China, Taiyuan, China.
authors: Shan
authors: S
authors: Du
authors: Yong
authors: Y
authors: Wang
authors: Li-Zhen
authors: LZ
authors: Chen
authors: Wen-Jing
authors: WJ
authors: Shi
authors: Fu-de
authors: FD
authors: Ren
authors: Yong-Xiang
authors: YX
authors: Li
authors: Jian-Long
authors: JL
authors: Wang
authors: Duan-Lin
authors: DL
authors: Cao
mesh_terms: D001608:Beryllium / Q000737:chemistry*; D002413:Cations, Divalent; D002414:Cations, Monovalent; D004583:Electrons; D053834:Explosive Agents / Q000737:chemistry*; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D011720:Pyrazoles / Q000737:chemistry*; D011789:Quantum Theory; D012964:Sodium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D002413:Cations, Divalent; D002414:Cations, Monovalent; D053834:Explosive Agents; D011522:Protons; D011720:Pyrazoles; D008094:Lithium; D012964:Sodium; D008274:Magnesium; D001608:Beryllium; D010100:Oxygen