论文部分内容阅读
在Cl→M(r)和M(r)→Cl两个方向电场作用下,采用密度泛函UBP86方法研究了线性杂金属串配合物[CuCuM(npa)4Cl]+(1:M=Pt,2:M=Pd,3:M=Ni)的几何和电子结构的变化规律.总体上,电场作用下高电势端原子的自旋密度减小而低电势端原子的自旋密度增大,原子的负电荷向高电势方向移动,分子能量下降,偶极矩呈线性变化;前线轨道分布呈规律性变化,随电场增大前线占据轨道能升高的显著性次序为πnb>σ*>δ*M(r)—N(r),这使前线占据轨道能级易交错.在Cl→M(r)电场作用下,自旋密度由Cu向杂金属M离域,Cu的正电荷向M转移;分子能量下降更显著;Cu—Cu和Cu—M键缩短,前线轨道能隙减小,利于金属链的电子传输.而M(r)→Cl电场则使Cu—Cu,Cu—M键增长,但对分子能量及金属原子的电荷密度和自旋密度的影响不明显,当增大至一定电场强度后金属原子的自旋密度保持不变,两个方向电场作用下自旋密度的变化呈明显的非对称性.故1～3可能具有分子整流器的潜在应用.
Under the action of the electric field of Cl → M (r) and M (r) → Cl, the density functional theory (UBP86) was used to study the effect of the linear complex metal complexes [CuCuM (npa) 4Cl] 2: M = Pd, 3: M = Ni). In general, the spin density of the atom at the high potential decreases and the spin density of the atom at the low potential increases with the increase of the atomic The negative charge moves toward the high potential, the molecular energy decreases and the dipole moment changes linearly. The frontal orbital distribution changes regularly. The order of significance of the occupied orbital energy increases with increasing electric field is πnb> σ *> δ * M (r) -N (r), which make the frontier occupy the orbital level easily staggered .In Cl → M (r) electric field, the spin density from Cu to the miscellaneous metal M delocalization, the positive transfer of Cu to M Cu-Cu and Cu-M bonds are shortened, the frontier orbital energy gap is reduced, which is conducive to the electron transport of the metal chain. However, the electric field of M (r) → Cl increases the Cu-Cu and Cu-M bonds , But it has no obvious effect on the charge energy and the charge density and the spin density of the metal atoms. When the electric field strength increases, the spin density of the metal atoms remains unchanged. The spin density Tumors had asymmetry. 1 to 3, it may have potential application of molecular rectifier.