CAJ | 학술논문

用 UBP86方法研究了金属串配合物[Cr3(dpza)4Cl2](1)和[Cr3(dpza)4(NCS)2](2)在外电场作用下的几何和电子结构的变化规律。发现随电场增大，高电势端的Cr-Cl和Cr-N键增长，而低电势端的Cr-Cl和Cr-N键缩短。轴向配体L的负电荷由低电势端向高电势端转移，1中原子的自旋密度变化很小，2中低电势端的Cr原子和L的自旋密度变化较明显。随电场增大，分子能量下降，偶极矩呈线性增大；HOMO和HOMO-1轨道能升高且轨道分布移向低电势端，相反，LUMO轨道能减小且轨道分布移向高电势端，使HOMO-LUMO能隙减小，有利于金属链的导电性。电场对2的上述结构和性质的影响尤为显著。
용 UBP86방법연구료금속천배합물[Cr3(dpza)4Cl2](1)화[Cr3(dpza)4(NCS)2](2)재외전장작용하적궤하화전자결구적변화규률。발현수전장증대，고전세단적Cr-Cl화Cr-N건증장，이저전세단적Cr-Cl화Cr-N건축단。축향배체L적부전하유저전세단향고전세단전이，1중원자적자선밀도변화흔소，2중저전세단적Cr원자화L적자선밀도변화교명현。수전장증대，분자능량하강，우겁구정선성증대；HOMO화HOMO-1궤도능승고차궤도분포이향저전세단，상반，LUMO궤도능감소차궤도분포이향고전세단，사HOMO-LUMO능극감소，유리우금속련적도전성。전장대2적상술결구화성질적영향우위현저。
The geometrical and electronic structures of string complexes [Cr3(dpza)4Cl2](1S) and [Cr3(dpza)4(NCS)2](2U) were investigated theoretically with density functional theory UBP86 method by incorporating the external electric field. The electric field results the elongation of Cr-Cl or Cr-N distances at the high potential end while the contraction at the low potential end. The negative charge of L (L=Cl, NCS) moves to the high potential side. The spin density of1S changes a little, while that of2U at the low potential side is sensitive to the electric field. With the increase of the electric field, the molecular energy decreases and the dipole moment increases linearly. Moreover, the spatial distributions of HOMO(σnb) and HOMO-1(πnb) move to the low potential end with the orbital energies increasing, while that of LUMO changes oppositely. This results in the decreasing of HOMO-LUMO gap which is beneficial to electron-transport properties of the metal string complexes. Above geometric and electric structures of2U are much more sensitive to the electric field than1S.