Zorn Deborah D, Boatz Jerry A, Gordon Mark S
Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
J Phys Chem B. 2006 Jun 15;110(23):11110-9. doi: 10.1021/jp060854r.
New energetic ionic liquids are investigated as potential high energy density materials. Ionic liquids are composed of large, charge-diffuse cations, coupled with various (usually oxygen containing) anions. In this work, calculations have been performed on the tetrazolium cation with a variety of substituents. Density functional theory (DFT) with the B3LYP functional, using the 6-311G(d,p) basis set was used to optimize geometries. Improved treatment of dynamic electron correlation was obtained using second-order perturbation theory (MP2). Heats of formation of the cation with different substituent groups were calculated using isodesmic reactions and Gaussian-2 calculations on the reactants. The cation was paired with oxygen rich anions ClO4-, NO3-, or N(NO2)2- and those structures were optimized using both DFT and MP2. The reaction pathway for proton transfer from the cation to the anion was investigated.
新型含能离子液体作为潜在的高能量密度材料受到研究。离子液体由大的、电荷分散的阳离子与各种（通常含氧化合物）阴离子组成。在这项工作中，对带有各种取代基的四唑阳离子进行了计算。采用密度泛函理论（DFT）中的B3LYP泛函，使用6 - 311G(d,p)基组来优化几何结构。利用二阶微扰理论（MP2）获得了对动态电子相关的改进处理。使用等键反应并对反应物进行高斯 - 2计算，得出了带有不同取代基的阳离子的生成热。该阳离子与富氧阴离子ClO4-、NO3-或N(NO2)2-配对，并使用DFT和MP2对这些结构进行了优化。研究了质子从阳离子转移到阴离子的反应途径。
