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本文用SCC-DV-X。法计算了O_5(CO)_6和O_sH_2(CO)_4两个分子的基态能级,Mulliken布屠分析,态密度和键级。O_s(CO)_5的最低空轨道与最高占据轨道的能级差为4.3eV,位于近紫外区。在O_s(CO)_5中,轴向羰基的σ轨道与O_s的dz~2之间足一种强排斥作用,电荷迁移计算说明σ馈键在O_s(CO)_5中起着重要的作用。对于O_sH_2(CO)_4,O_s的dz~2与H_2的la轨道,O_s的dxz轨道与H_2的1b轨道间的相互作用削弱了H-H,稳定生成O_s-H键。键级数据表明,O_sH_2(CO)_4在双聚反应中,轴向CO首先离解,而后是H的双核消除;CO的对位削弱键的影响效应要比H的强。
In this paper, SCC-DV-X. The ground states, Mulliken distribution, density of states and bond order of two molecules O_5 (CO) _6 and O_sH_2 (CO) _4 were calculated. The difference in energy level between the lowest empty orbit and the highest occupied orbit of O_s (CO) _5 is 4.3 eV, which is located in the near ultraviolet region. In O_s (CO) _5, there is a strong repulsion between the sigma orbitals of axial carbonyls and dz ~ 2 of O_s. The charge transfer calculations show that the σ-feed bond plays an important role in O_s (CO) _5. For the la orbitals of dz ~ 2 and H_2 of O_sH_2 (CO) _4, O_s, the interaction between the dxz orbit of O_s and the 1b orbit of H_2 weakens H-H and generates O_s-H bonds stably. Key-level data indicate that in the dimerization reaction of O_sH_2 (CO) _4, the axial CO dissociates firstly and then the dual nuclei of H are eliminated. The effect of CO on the para-weakening bond is stronger than that of H.