大学毕业设计---hs与ho2水催化气相反应机理的理论研究.docVIP

HS与HO2水反应机理的理论研究（陕西师范大学化学与材料科学学院, 西安, 710062）摘要 应用密度泛函理论B3LYP方法对HS自由基与HO2自由基有、无水催化的微观反应机理进行了研究, 在B3LYP/6-311+G(2df,2p) 水平上优化了反应通道上各驻点（反应物、中间体、过渡态和产物）的几何构型, 并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态结构及连接性进行了验证. 采用CCSD(T)/6-311++G(3df,2pd) 方法对所有驻点进行了单点能校正, 构建了有水、无水分子参与情况下HS与HO2气相反应体系的单、三重态反应势能剖面. 研究结果表明, HS与HO2反应体系在无水分子参与情况下的优势通道发生在三重态势能面上, 其表观活化能为-1.17 kcal(mol-1. 有水分子参与情况下存在2条反应通道共9条反应路径, 优势路径RW→1TS2→3PW(H2S-H2O+3O2)发生在三重态势能面上, 其表观活化能为-3.82 kcal(mol-1, 是一个无势垒氢迁移过程, 水分子产生了2.65 kcal(mol-1的催化作用. 关键词 HS; HO2; 密度泛函理论(DFT)反应机理Abstract The mechanism for the reaction of HS with HO2 was investigated at the B3LYP/6-311+G(2df,2p) level on the singlet and triplet potential energy surface. All the stationary points involved in the title reaction were calculated at the B3LYP/6-311+G(2df,2p) level. Frequency calculation and intrinsic reaction coordinate (IRC) analysis at the same level were applied to validation of the connection of transition states to reactants and products. The single points energies of all the stationary points are refined at the CCSD(T)/6-311++G(3df,2pd) level of theory. The results show that the major channel of HS+HO2 system without water happened on the triplet potential energy surface, apparent activation energies separately is -3.82 kcal(mol-1. The situation water participationhas two dominating reaction channels(nine pathways), The major channel R→1TS2→3PW(H2S-H2O+3O2) happened on the triplet potential energy surface, apparent activation energies separately is -3.82 kcal(mol-1, and domain path is a barrierless process, the water molecule produces a catalytic effect of 2.65 kcal(mol-1. Keywords HS; HO2; Density Functional Theory (DFT); Catalytic Effects of a Single Water Molecule; Reaction Mechanism; Transition State Theory.目 录 摘 要 . I Abstract. I 简 介 1 1 计算方法 2 2 结果与讨论 3 2.1 单水分子对催化作用 4 2.1.1无水条件下的反应 4 2.1.2 HO2、HS自由基与水形成的氢键复合物 6 2.2水催化条件下的单重态反应 7 2.2.1双氢原子转移 7 2.2.2抽氢反应 7 2.3水催化条件下的三重态反应 9 2.3.1双氢原子转移 9 2.3.2抽氢反应 9 2.3.3电子转移质子耦合 10 2.4主反应通道优势路径中键长随反应坐标的