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Evaluating the Activation Barriers for Transition Metal N_2O Reactions

机译:评估过渡金属N_2O反应的活化势垒

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摘要

The reactions of 3d transition metal atoms with N_2O,producing the metal oxide and N_2,have been studied by means of density functional theory and the coupled cluster method CCSD(T).The importance of charge transfer in the reaction mechanism has been investigated.For Sc,Ti,and V,the transition state is very reagent-like,and almost no charge transfer occurs.On the other hand,charge transfer from the metal 4s orbital into the N_2O LUMO becomes more important when moving to the right in the 3d series.The reactions with Sc,Ti,and V proceed almost without energy barriers,whereas for Mn,Fe barriers around 9 kcal/mol are calculated.For transition metal atoms with a 3d~n4s~2 ground-state configuration,a correlation is found between the activation barriers and the binding energy of the formed metal oxide.The 3d~(n+1)4s~1 configuration gives rise to a higher reactivity than the 3d~n4s~2 configuration.
机译:利用密度泛函理论和耦合簇方法CCSD(T)研究了3d过渡金属原子与N_2O的反应生成金属氧化物和N_2,研究了电荷转移在反应机理中的重要性。 Sc,Ti和V的过渡态非常像试剂,几乎没有电荷转移发生。另一方面,当3d向右移动时,从金属4s轨道到N_2O LUMO的电荷转移变得更加重要。与Sc,Ti和V的反应几乎没有能垒,而对于Mn,Fe的势垒约为9 kcal / mol。对于具有3d〜n4s〜2基态构型的过渡金属原子,相关性为3d〜(n + 1)4s〜1构型比3d〜n4s〜2构型产生更高的反应活性。

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