A Screened Hybrid Density Functional Study on Energetic Complexes: Metal Carbohydrazide Nitrates

The molecular geometry, electronic structure and thermochemistry of a series of metal carbohydrazide nitrates were investigated using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional. The results show that Ca, Sr, and Ba complexes have additional coordinated oxygen atoms from the nitrate ion, which differ obviously from Cu, Ni, Co, and Mg complexes in terms of the geometric structure. Detailed NBO analyses clearly indicate that the metal-ligand interactions in Cu, Ni, and Co complexes are covalent, whereas those of Mg, Ca, Sr, and Ba complexes are ionic in nature. Furthermore, the donor-acceptor interactions result in a reduction of occupancies of sigma(C-O) and sigma(N-H) orbitals. Consequently, the bond lengths increase and the bond orders decrease. Finally, the calculated heats of formation predict that the ionic alkaline-earth metal carbohydrazide nitrates are more stable than the covalent transition metal carbohydrazide nitrates. It agrees well with the available experimental thermal stabilities, indicating that the metal-ligand bonding character plays an important role in the stabilities of these energetic complexes. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 2311-2316, 2011