title: A screened hybrid density functional study on energetic complexes: cobalt, nickel and copper carbohydrazide perchlorates.
abstract: The molecular geometry, electronic structure, infrared spectra and thermochemical properties of cobalt and nickel tris(carbohydrazide) perchlorates (CoCP and NiCP) as well as copper bis(carbohydrazide) perchlorate (CuCP) were investigated using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional. The results show that both perchlorate ions coordinate with the copper atom, and the interactions between copper and perchlorate are ionic, whereas all the metal-carbohydrazide interactions are covalent. Due to the delocalization from the sigma(N-H) bond orbital to the n*(M) antibond orbital, the amino stretching vibrations of these complexes show considerable red-shift compared with those of free carbohydrazide ligand. The calculated heats of reaction and formation indicate that the formations of these complexes are exothermic, and the order of their thermal stability is NiCP>CoCP>CuCP. These agree well with the experimental results. Finally, we find that there is a relationship between the energy gap and impact sensitivity.
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China.
authors.forename: Huisheng
authors.initials: H
authors.lastname: Huang
authors.forename: Tonglai
authors.initials: T
authors.lastname: Zhang
authors.forename: Jianguo
authors.initials: J
authors.lastname: Zhang
authors.forename: Liqiong
authors.initials: L
authors.lastname: Wang
mesh_terms: D000465:Algorithms; D003035:Cobalt / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry; D006834:Hydrazines / Q000737:chemistry*; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010472:Perchlorates / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics
chemical_list: D006834:Hydrazines; D010472:Perchlorates; D003035:Cobalt; D003300:Copper; D009532:Nickel; C019289:carbohydrazide