采用多种量子化学方法对缓蚀剂哌啶（PD）进行计算，由构象转变能垒确定了分子的吸附构象。以O-Fe-O和O-Cr-O-Cr-O模拟氧化膜的一维链，施行量子化学从头算（ab initio)研究，得到了分子的稳定构型及电子结构。根据化学反应普遍微拢理论（GPT）分析缓蚀剂与氧化膜的作用方式。结果表明，哌啶在氧化膜表面的作用属于电荷控制反应，通过N原子与金属原子之间授受电子形成配位键实现吸附取向。
Three kinds of quantum chemistry methods, semiemperical SCF/PM3(improved MNDO)and ab initio SCF/STO-3G and SCF/6-31G,were applied to clarify the origin of the good inhibition performance of piperidine (PD) on passive film of stainless steel.According to the data of formation heat and absolute energy of molecules with different possible conformation,the chair style conformation of PD is stable.With O-Fe-O-Fe-O and O-Cr-O-Cr-O being succedaneums of one dimension oxide film,the optimized geometry and electron energy level of these molecules were calculated by ab initio SCF/STO-3G.On the basis of chemical reaction generalized perturbation theory,the interaction between inhibitor PD and metal oxide was discussed.The results indicated that the adsorption of PD on passive film is a charge control reaction.The adsorption of PD can be ascribed to N atom acting as electron donor to chalets with Fe and Cr atoms in oxide film. The obtained adsorpton bond energy is in agreement with the single bond energy of normal Fe, Cr complexes including nitrogen aton.Moreover,the adsorption orientation of PD on passive film was deduced preliminarily.
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