一氯氧化物及其负离子的分子结构和热力学性质

Molecular structures and thermodynamics of mono-chlorine oxides and anions

利用两种杂化DFT方法(BHLYP和B3LYP,两种纯DFT方法(BP86和BLYP),以DZP++为基函数对ClOO,ClOOO和ClO3及其负离子的平衡构型进行了量子化学计算,研究了它们的几何构型、相对能量、三种电子亲和势(绝热电子亲和势Ead=E(optimizedneutral)-E(optimizedanion),垂直电子亲和势Evert=E(optimizedneutral)-E(anionatneutralequilibriumgeometry)和垂直电子解离能Evd=E(neutralatanionequilibrium)-E(optiminzedanion))和红外振动频率.

The molecular structures and total energies of ClOO, ClOOO and ClO3 have been studied using four independent density functional theory methods. Optimized geometries, adiabatic electron affinities, vertical electron affinities, vertical detachment energies are reported. Harmonic vibrational frequencies are also reproted. Among these Four density functional methods, the unrestricted BHLYP and B3LYP methods used for the open-shell ClOO and ClOOO system lead to the serious spin contamination, while the BLYP and BP86 methods have only little spin contamination (<S2><0.76). The reliable predicted adiabatic electron affinities with BLYP method are 3.33 eV (ClOO), 3.97(ClO3) and 2.84 eV(ClOOO). The electronic ground state of ClOO- is a triplet (3 A″) state. There are seven local minima on the potential energy surface for ClOOO-, among them the gauche structure is the global minimum. The ClOO- and ClOOO- ground state might be regarded as Cl-...O2 and Cl-...O3 complex, respectively. The ClOO- anion triplet state lies below OClO- by 205-217 kJ/mol (BP86 and BLYP). The ClOOO isomer is predicted to lie below 222-238 kJ/mol (BP86 and BLYP) below the C3v structure ClO3. The gauche-ClOOO- is predicted to lie 131.3 kJ/mol (BLYP) below ClO-3 (C3v) structure.