| Ru催化N2与H2反应合成氨的两态反应机理 |
| Two-State Reaction Mechanism Ammonia Synthesis from of N2 and H2 Catalyzed by Ru |
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| 摘要: 采用密度泛函理论（DFT） UB3LYP方法对Ru在单重态、三重态及五重态势能面上催化N2与H2反应合成氨的两态反应机理进行理论研究，发现该反应为典型的两态反应。计算得到最低能量交叉点（MECP）处自旋-轨道耦合常数（Hsoc）及双程系间窜越几率（PISC），MECP1：Hsoc=508.34 cm-1，P2ISC=0.85，MECP9：Hsoc=269.21 cm-1，P2ISC=0.27。运用能量跨度模型（energetic span model）确定Ru催化合成氨反应的转化频率（TOF）决速过渡态（TDTS）为3TS2-3，TOF决速中间体（TDI）为3IM9。 |
| 关键词: 合成氨 两态反应 自旋-轨道耦合 系间窜越几率 最低能量交叉点 |
| 基金项目: 国家自然科学基金（No.21263023）资助。 |
| Abstract: The two-state reaction mechanism of NH3 synthesis from N2 and H2 catalyzed by Ru are theoretical studied on the singlet, triplet and quintet potential energy surface, and the density functional theory (DFT) UB3LYP methods was used, which is a typical two-state reaction. We calculated spin-orbital coupling constant (Hsoc) and intersystem crossing probability (PISC) at minimum energy crossing point (MECP) respectively, for MECP1:Hsoc=508.34 cm-1, P2ISC=0.85; for MECP9:Hsoc=269.21 cm-1, P2ISC=0.27. We used energy span model to determine that turnover frequency (TOF)-determining transition state (TDTS) of the reaction is 3TS2-3 and TOF-determining intermediate (TDI) of the reaction is 3IM9. |
| Keywords: synthetic ammonia two-state reaction spin-orbital coupling intersystem crossing probability minimum energy crossing point |
| 投稿时间：2021-01-31 修订日期：2021-06-25 |
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| 吴晶晶,王永成,康娟霞.Ru催化N2与H2反应合成氨的两态反应机理[J].无机化学学报,2021,37(9):1536-1546. |
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