【摘要】 用密度泛函B3LYP/6-31G**计算方法,对不同碳链长度和不同氧化态( V2 +/V+.)紫罗碱二硫醇的平衡几何构型及相应电子结构的研究表明,两种氧化态在吡啶环共面性和前线轨道电子集居上的差异与特征,导致氧化态V2 +成为紫罗碱亲合金原子形成Au-S-nVn-S-Au结构的关键组分,自由基V+.则在该结构的氧化还原电子传导中发挥核心作用.S-S核间距与前线轨道能隙的计算结果表明,在紫罗碱二硫醇单分子电导的测量中,亚甲基数n达到12的分子长度是有效的.更多还原

【Abstract】 The equilibrium geometry and the electronic structure of a viologen dithiols for different alkane chain lengths and different oxidation states by density function B3LYP/6-31G has benn calculated.There are different characters in the dihedral angle for a bipyridinium and in the frontal orbital population between the oxidation state V2+ and V+·.The oxidation state V2+ is key constituent when bond between the viologen molecule and Au atom to form Au-S-V-S-Au system.The free radical V+· have an mainly effect on the redox electronic transport,As a result of the calculation results of the S-S distance and energy Egap between HOMO(V+·) and LUMO(V2+),the molecular length containing 12 carbon atom is shown to be effective on measurement of the single-molecule conductivity of a viologen dithiol.更多还原