基于广义梯度近似密度泛函和全势能线性缀加平面波方法,本文对聚铜络合物[Cu(L)μ-1,3-N3]n(ClO4)n(其中L=tridentate Schiff base为三齿席夫基)的态密度和磁矩进行了计算.磁矩计算结果表明:①该聚铜络合物晶体格子的总磁矩为1.00 μB;②中心铜原子(离子)具有最大的原子磁矩,为0.531 μB;③铜原子和它周围最邻近的氮原子的原子磁矩是该聚铜络合物晶体格子总磁矩的主要来源.通过对中心铜原子及其最邻近氮原子的自旋态密度图进行分析,得出了铜原子和它周围最邻近氮原子的磁性主要分别来源于它们的d轨道和p轨道,同时还发现了中心铜离子的d轨道与叠氮末端氮原子的p轨道之间存在杂化现象, 以及中心铜离子向叠氮末端氮原子的自旋退局域化现象.自旋退局域化效应通过叠氮这一旁道使相邻两中心铜离子发生铁磁性相互作用.

Based on density functional theory (DFT) with the generalized gradient approximation (GGA) and a full-potential linearized augmented plane wave (FP-LAPW) method, the calculation of the electronic structures and the magnetic properties on [Cu(L)μ-1,3-N3]n(ClO4)n, where L is the tridentate Shiff base, has been performed. The results of magnetic moment calculation indicate:① the total magnetic moment of a cell is 1.00 μB; ②the Cu atom has a largest magnetic moment of 0.531 μB;③the contributions of the total magnetic moment mostly come from the central Cu atom and its first coordination N atoms. By studying the density of states (DOS) of the Cu atom and the N atoms, the magnetism of the Cu atom and the N atoms mainly coming from the Cu 3d orbital and the N 2p orbital respectively is revealed; the hybridizations occurring between the d orbital of the central Cu atom and the p orbital of the azido terminal nitrogen atoms are found; a spin delocalization from the Cu atom towards the N atoms of the azido terminal is also found. Through the azido pathway, the spin delocalization makes the neighboring Cu atoms having ferromagnetic interaction.