摘要
用Gaussian03W程序在B3LYP/631G和HF/631G水平上对二苯二硫(DPDS)和二苄二硫(DBDS)的分子几何构型、电子结构、分子轨道指数及与铁原子簇的相互作用等进行了理论计算.用前线分子轨道理论分析了反应的活性原子和活性键,讨论了DPDS和DBDS与铁原子的作用方式,用前线电子密度,超离域性指数,原子净电荷及化合物与铁原子簇的化学吸附作用能等参数作为判据分析了DPDS和DBDS与铁原子间键合的强弱,反应性的大小.计算结果表明DPDS和DBDS与铁接触时,趋向于S-S键与C-S键断裂,在较为缓和的摩擦条件下,DPDS的抗磨作用优于DBDS,在较为苛刻的摩擦条件下,DBDS的极压作用优于DPDS,与摩擦学试验结果一致.
The molecular geometries optimization and electronic structures of diphenyl disulfide （DPDS） and dibenzyl disulfide （DBDS） compounds were investigated by density functional theory （DFT） and ab initio method at the 6-31G^＊ basis set level. The active atoms and bonds of reaction were provided by frontier molecular orbital theory. The molecular orbital parameters of DPDS and DBDS compounds and iron atom cluster were calculated by using density functional theory. The interaction pattern between the organic disulfide compounds and iron atom cluster was discussed based on the approximate rule of orbital energy. Some parameters characterizing the action strength between the organic disulfide compounds and iron atom cluster, including the bonding strength, reactive strength and static action strength, were analyzed by using frontier electron density, super de-iocalizability, net atomic charge and the interaction energy of chemical adsorption as criteria. The results indicate that S-S chemical bond and C-S chemical bond of the compounds are inclined to be broken when DPDS and DBDS interact with the metal. The anti-wear ability order of DPDS and DBDS compounds is DPDS 〉 DBDS, and the extreme pressure ability order of DPDS and DBDS compounds is DBDS 〉 DPDS, and the prediction results based on quantum chemistry calculations are in good accordance with the friction and wear test results.
基金
ProjectsupportedbytheNationalNaturalScienceFoundationofChina(50005018)
HunanProvincialNaturalScienceFoundationofChina(02JJY2019)andHunanProvincialMidyouthScienceandTechnologyFoundationofChina(04JJ1010)
