Plowright Richard J, McDonnell Thomas J, Wright Timothy G, Plane John M C
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD UK.
J Phys Chem A. 2009 Aug 20;113(33):9354-64. doi: 10.1021/jp905642h.
Optimized geometries and vibrational frequencies were calculated for Mg+-X and [X-Mg-Y]+ complexes (X, Y = H2O, N2, CO2, O2, and O), required for understanding the chemistry of magnesium in the upper atmosphere. B3LYP optimizations were performed employing 6-311+G(2d,p) basis sets. In several cases a number of different orientations were investigated in order to determine the geometries of lowest energy, and in cases involving O and O2, different spin states also had to be considered. In contrast to the corresponding Ca+-containing complexes, the diligated Mg+ ions have the two ligands approaching from the same side. In order to establish accurate energetics, up to RCCSD(T) single-point energy calculations were also employed, using quadruple-zeta basis sets. Accurate dissociation energies for the Mg+-X and [X-Mg-Y]+ species were derived and discussed. Comparison with available experimental results was made where possible.
为了理解高层大气中镁的化学性质，计算了Mg⁺-X和[X-Mg-Y]⁺配合物（X、Y = H₂O、N₂、CO₂、O₂和O）的优化几何结构和振动频率。使用6-311+G(2d,p)基组进行B3LYP优化。在几种情况下，研究了许多不同的取向以确定能量最低的几何结构，并且在涉及O和O₂的情况下，还必须考虑不同的自旋态。与相应的含Ca⁺配合物不同，配位的Mg⁺离子有两个配体从同一侧接近。为了确定准确的能量，还使用四重zeta基组进行了高达RCCSD(T)的单点能量计算。推导并讨论了Mg⁺-X和[X-Mg-Y]⁺物种的准确解离能。在可能的情况下与现有实验结果进行了比较。
