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检测现有的Cu~(2+)氧盐矿物结构表明:有一些Cu~(2+)φ_n(φ=O~(2-),OH~-,H_2O;n=4,5,6)配位多面体是(4+2)畸变八面体、四方锥体、三角双锥体和平面四方形的几何构型之间的过渡类型。Cu~(2+)氧盐矿物中存在着(4+2)畸变八面体与四方锥体、(4+2)畸变八面体与平面四方形、四方锥体与平面四方形之间的结构变化途径。用Hartree-Fock分子轨道的STO-3G基集计算(Cu~(2+)φ_n)~(-n+2)模型分子壳来研究其壳的配位结构和可能的结构变化途径的能量。计算结果表明:沿(4+2)畸变八面体到平面四方形途径存在着小的能垒,从(4+2)畸变八面体到三角双锥体途径存着大的能垒,但在这两个标准的配位结构之间沿着另一个可能结构变化途径不存在能垒。其计算结果与矿物中所获得的Cu~(2+)φ_n结构很好地一致。该研究显示Cu~(2+)配合物应解释为完全对称的配位结构之间结构变化途径上的配合物。
The detection of the existing Cu ~ (2+) oxysalt shows that some Cu ~ (2+) φ_n (φ = O ~ (2 -), OH ~ -, H_2O, n = 4,5,6) A polyhedron is a type of transition between (4 + 2) distorted octahedra, tetragonal pyramids, trigonal pyramids, and planar tetragonal geometric configurations. (4 + 2) distorted octahedra and tetragonal pyramids, (4 + 2) distorted octahedra and planar tetragons, tetragonal pyramids and planar tetragons exist in Cu ~ (2+) oxysalt minerals way. The energies of the shell coordination structure and possible structural change pathways were calculated by using the STO-3G basis set of the Hartree-Fock molecular orbitals to calculate the Cu 2+ (2+) n_n-2 model shell. The calculated results show that there is a small energy barrier along the (4 + 2) distorted octahedron to the square tetragonal path, and a large energy barrier exists from the (4 + 2) distorted octahedron to the triangular double pyramidal pathway. However, There is no energy barrier along the path of another possible structural change between the two standard coordination structures. The calculated results are in good agreement with the Cu ~ (2+) φ_n structure obtained in minerals. This study shows that Cu 2+ complexes should be interpreted as complexes of the structural change between fully symmetric coordination structures.