【摘要】 该文是硝酸酯的分子几何、电子结构以及水解机理之系列研究的第Ⅰ报。用ＭＩＮＤＯ／３、ＭＮＤＯ、ＡＭ１和ＰＭ３４种分子轨道方法，全优化得到硝酸甲酯的平衡几何、净电荷和键级，结果彼此相符，以ＡＭ１法稍好。用ＡＭ１法求得硝酸甲酯的碱性水解位能曲线；研究了反应体系的几何构型和电荷分布随反应坐标的变化；求得活化能为５１．３３ｋＪ／ｍｏｌ，比以前的计算值（５．７０ｋＪ／ｍｏｌ）更接近实验值（８２．４０ｋＪ／ｍｏｌ）。更多还原

【Abstract】 This paper is the first one about research of molecular geometry,electronic structure and mechanism of hydrolysis for nitrates, The equilibrium geometry,net charge on atoms and bond orders between atoms in molecule of methyl nitrate have been obtained by means of four MO methods,namely MNDO,AM1 and PM3,through completely optimized calculations,The calculated results from various methods are corresponding to each other and show that the AM1 method is a little better than the others.Applying AM1 calcula-tions,the potential curve, geometry change curve and charge change curve along the reaction coordinate in the alkaline hydrolysis of methyl nitrate were given. The activation energy by AM 1 calculation equal to 51.33kJ/mol,which is more approximate to the experimental value(82.42 kJ/mol) than previous calculation(5.70kJ/mol).更多还原