Comparative DFT study of [Mg(CHZ)₃](ClO₄)₂ and [Mg(CHZ)₃](NO₃)₂ (CHZ=Carbohydrazide)

Abstract

The molecular geometry, electronic structure, thermochemistry and infrared spectra of [Mg(CHZ)₃](ClO₄)₂ and [Mg(CHZ)₃](NO₃)₂ were comparatively studied using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional with 6–31G** basis set. The experimental results show that the complexes have six-coordinated octahedron feature, and the metal-ligand interactions are predominantly ionic in nature. The calculated heats of formation predict that [Mg(CHZ)₃](NO₃)₂ is more stable than [Mg(CHZ)₃](ClO₄)₂. Detailed NBO analyses indicate that the ligand-anion interaction plays an important role in the stability for these two energetic complexes. Moreover, the stretching vibration frequencies of N-H bonds shift to lower wave number compared to the free CHZ ligand, which are caused by the delocalizations from N-H bond orbital to lone-pair electron antibond orbital of magnesium.

Keywords

energetic complex / carbohydrazide / density functional theory / electronic structure / heats of formation

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