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气相钌原子与氮分子作用机理计算研究
引用本文:王朝杰,王燕妮,金芩,孙晓玲,蔡跃飘.气相钌原子与氮分子作用机理计算研究[J].原子与分子物理学报,2016,33(6).
作者姓名:王朝杰  王燕妮  金芩  孙晓玲  蔡跃飘
作者单位:温州医科大学,温州医科大学药学院,温州医科大学药学院,温州医科大学药学院,温州医科大学
摘    要:运用B3LYP/6-311+G*(LANL2DZ)详细地研究了Ru原子与N2分子相互作用的单端位直线型L-RuN2和单侧双配位S-RuN2及插入化合物NRuN弯曲型和直线型的不同自旋多重度下多个电子态的平衡几何结构、电子结构、轨道布居和振动光谱等性质,同时对构型转化和插入反应过渡态及反应的势能曲线进行了计算. 结果表明两种构型的复合物中一般低能态Ru对N2的活化都不大,直线型的3和3-相对基态反应物是能稳定存在的,轨道作用机制是授予与反馈. 化合物NRuN与实验对照,13B1和11A1态可能是实验所观察的,两种构型中众多电子态相对于Ru(a5F)+2N(4S)是稳定的. 势能曲线体现插入反应能垒很高,生成NRuN化合物在热力学和动力学上都是不利的.

关 键 词:Ru原子  N2分子  插入反应  势能曲线  密度泛函方法

Theoretical study on the interaction mechanism of ruthenium atom with nitrogen molecule in gas phase
WANG Chao-Jie,and.Theoretical study on the interaction mechanism of ruthenium atom with nitrogen molecule in gas phase[J].Journal of Atomic and Molecular Physics,2016,33(6).
Authors:WANG Chao-Jie  and
Institution:Wenzhou Medical University,,,,
Abstract:The geometrical and electronic structures, bonding properties, and vibrational frequencies of complex RuN2 and compound NRuN in linear and bent structures with different multiplicity and electronic states were studied by B3LYP method using 6-311+G* and LANL2DZ basis sets. The transition states for transformation between linear and bent structures and insertion reaction were calculated, and the potential energy curves obtained. The results indicate that N2 molecule was activated slightly in most stable electronic states of the complexes, 3 and 3- states are more stable than the ground states of the reactants. There were some electrons transferred from Ru atom to N2 molecules via donation and backing. Compared to experiment reported, the structure and vibrational characteristics of compound NRuN in 13B1 and 11A1 states are agreed well and proposed as the plausible candidates for the experimental result. Most of electronic states of compound NRuN formed from Ru(a5F)+2N(4S) are exothermic. Ru atom direct insertion into the triple bonds N2 is much more difficult because the energy barriers are higher and the products are thermodynamic instability.
Keywords:Ruthenium atom  Nitrogen molecule  Insertion reaction  Potential energy curves  Density functional theory
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