Ti,Na与O2反应机理的理论研究

Theoretical Study of Reaction Mechanism of Ti,Na with O_2

基于MP2/6-311+G(d)水平,分别对过渡金属Ti和碱金属Na与O2的反应机理进行了研究.比较了Ti和Na分别以垂直O—O键和沿着O—O键的方向逼近O2,以及中性体系Ti/Na+O2和带1个负电荷的体系(Ti/Na+O2)-的情况.详细分析了不同反应路径的结合能和电荷变化的曲线,预测了最佳反应方式.结果表明,垂直接近方式要比水平接近方式更具有优势;体系带一个负电荷(Ti/Na+O2)-有利于金属与O2的结合.同时,计算结果表明在Ti+O2和(Ti+O2)-体系中Ti容易与单态的O2结合;在中性体系中Na也容易与单态O2结合,而在(Na+O2)-体系中Na与三态O2的结合更稳定.在CCSD(T)/6-311++G(3df)//MP2/6-311+G(d)水平下,计算了Ti+O2和(Ti+O2)-的反应势能面.

The reaction mechanisms of Ti,Na with O2 were investigated at the MP2/6-311＋G（d）level.Ti and Na atom were assumed to approach O2 in the manner of horizontally or vertically with respect to the O—O bond,respectively.Both neutral Ti/Na＋O2 and anionic（Ti/Na＋O2）-systems were considered.The binding energy and the charge curves for each reaction pathway were analyzed in detail,to validate the optimal reaction mode.The reaction of metal atom（Ti and Na）with O2 is easier in negatively charged system（Ti/Na＋O2）-than the neutral Ti/Na＋O2,and the vertical pathway is more favorable than the horizontal.Meanwhile,the calculated results show that Ti atom prefers to react with the singlet O2 in both neutral and negatively charged systems.Na is easy to react with the singlet O2 in the neutral system,but with triplet O2 in negatively charged system.The potential energy surface of Ti with O2 reaction was also calculated at CCSD（T）/6-311＋＋G（3df）//MP2/6-311＋G（d）for Ti＋O2 and（Ti＋O2）-systems.