多种密度泛函方法对NpO2+离子研究

用五类23种密度泛函方法在相对论有效势基组和6-311+G(d)水平上对NpO₂⁺的几何结构、电子结构和振动光谱进行计算研究，数据分析得到：(1) BLYP、G96LYP和B1B95方法不适合该离子的几何结构计算，其余密度泛函方法计算的键长值较合理，如BHandHLYP和B3LYP；(2) 在振动光谱计算方面，BLYP、G96LYP和MPWPW91方法不适用该体系研究，计算值偏低较多，VSXC和B98方法计算值与文献值吻合，其余方法计算结果相近；(3) 该离子的布居分析中，NBO的布居分析数据比Mulliken布居分析值更接近化学直观，而BHandH和BHandHLYP方法计算的离子前线轨道能差最大。

Various Density Functional Methods Study onNpO2+

The geometrical structure, electronic structure, and vibrational spectra of NpO₂⁺ were studied by means of 5 types including 23 kinds of density functional methods using relativistic effective potential together with double zeta basis sets for Np and 6-311+G（d） for O. Various DFT methods data show that: (1) the BLYP, G96LYP and B1B95 methods cannot be suited for the ion bond length, the other methods including the BHandHLYP and B3LYP are in good agreement with experimental values; (2) the vibrational frequencies calculated by the BLYP, G96LYP and MPWPW91 methods are much lower than plausible values, the others are consistent with reported values, especially the VSXC and B98 values; (3) to the population analysis data, the NBO population data are more intuitive compared with the Mulliken population data, furthermore, the frontier orbitals energy difference obtained by the BHandH and BHandHLYP methods are higher than others’ values.