【摘要】 取两种不同基组（含和不含Re的6p轨道）,用DV—X_α原子簇方法计算了[ReH₉]^2-阴离子和晶体K₂ReH₉的电子结构。结果表明,[ReH₉]^2-中的Re-H键本质上是Re 5d—H1s相互作用,Re原子的6s和6p轨道对Re-H成键影响不大。把[ReH₉]^2-阴离子嵌入一个具有空区的较大原子簇,模拟了K₂ReH₉离子晶体中的长程库仑势,使得计算的禁带宽度减小,并且较好地解释了电子吸收光谱实验结果。更多还原

【Abstract】 Electronic structures for [ReH₉]^2- anion and its crystal K₂ReH₉ have been calculated using the DV-X_α cluster method. Two different basis sets with and without the 6p atomic orbitals of Re atom have been adopted in the calculations. Results show that the Re-H bond mainly consists of Re 5d atomic orbitals and ls orbital of the ligand hydrogen atoms. Contribution from 6s and empty 6p atomic orbitals for rherium atom to the bonded molecular orbitals of this anion is little or nothing. Thus, the Re5d-H1s interaction is a characteristics of the Re-H bond in the [ReH₉]^2- anion. An anion of [ReH₉]^2- is embeded into a larger cluster with a empty rigion to simulate the long-range coulombic potential in the ionic crystal. The calculated band gap is decreased. The electronic spectroscopy of the K₂ReH₉ crystal has been reasonably interpreted.更多还原