FeO催化N2与H2反应生成NH3的理论研究

A theoretical study for the synthesis of ammonia in reaction of N2 and H2 catalyzed by FeO

本文采用密度泛函理论(DFT)UB3LYP方法对Fe O在基态五重态及第一激发态三重态势能面上催化N2与H2反应生成NH3的两态反应机理进行了研究,运用非共价作用预测反应位点,并运用分子中的原子(AIM)、电子定域化函数(ELF)及前线分子轨道理论对部分最低能量路径及最低能量交叉点(MECP)的机理进行了分析.计算了MECP处的自旋轨道耦合值(Hsoc)及系间窜越几率(PISC),通过应用能量跨度模型(energetic span model)确定了反应决速态,并从理论层面计算得到了反应中Fe O的催化转化频率(TOF).

Density functional theory(DFT)UB3 LYP methods was used for FeO catalytic N2 and H2 to synthesize ammonia in the quintet and triplet spin-state potential energy surfaces(PESs). By noncovalent interactions to predict reaction sites, the bonding properties of part of the species along the reaction were analyzed by electron localization function(ELF) and atoms in molecules(AIM), and the mechanism of minimum energy cross point(MECP) was analyzed by frontier molecular orbital theory. The spin-orbit coupling(SOC) and probability of intersystem crossing of different potential surfaces were discussed. In addition, this work demonstrated the reaction rate-determining step and calculated TOF by applying the energetic span model in theory.