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运用B3LYP/6-311+G*(LANL2DZ)详细地研究了Ru原子与N_2分子相互作用的单端位直线型L-Ru N_2和单侧双配位S-Ru N_2及插入化合物NRu N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N_2的活化都不大,直线型的3Δ和3∑-相对基态反应物是能稳定存在的,轨道作用机制是σ/π授予与反馈.化合物NRu N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(a~5F)+2N(~4S)是稳定的.势能曲线体现插入反应能垒很高,生成NRu N化合物在热力学和动力学上都是不利的.
The single-site linear L-Ru N 2 and one-sided bidentate S-Ru N 2 with the Ru atom interacting with N 2 molecules and the NRu N bending type of the intercalation compound were studied in detail using B3LYP / 6-311 + G * (LANL2DZ) Equilibrium geometry, electronic structure, orbital population and vibrational spectra of multiple electron states with different spin multiplicity under the different linearities were calculated. At the same time, the potential energy curves of transition state and reaction of the configuration transition and insertion reaction were calculated. The results show that the general low-energy state Ru has little activation of N 2, and the linear 3Δ and 3Σ-relative ground-state reactants are stable. The orbital mechanism is σ / π grading and feedback .Compound NRu N and the experimental control, 13B1 and 11A1 states may be experimentally observed, the two configurations of many electronic states relative to Ru (a ~ 5F) +2 N (~ 4S) is stable. Potential energy curve embodies the insertion reaction The energy barrier is high, and the formation of NRu N compounds is both thermodynamically and kinetically unfavorably.