Tersoff-Hamann and Bardeen perturbation theory derived empty-state STM images of the [4 + 2] intradimer adduct of 1,3-cyclohexadiene (CHD) adsorbed on Si(100)-2 x 1 using a density functional description of the electronic structure appear to capture the π~* C=C orbital observed experimentally but ultimately produce images dominated by the CH2 groups. Neither averages over finite temperature structures nor use of W(110) tips with O or Si adsorbed on the apex yield the correct image. Strong tip-CHD interactions substantially lower the energy of the π~* orbital relative to the Fermi energy and change the CHD geometry. In addition to perturbing the C=C bond, it is found that the tip pushes aside the CH2 groups. The former electronic effect enhances the prominence of the π~* orbital, while the latter geometric effect suppresses contributions from the remainder of the CHD.
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机译:Tersoff-Hamann和Bardeen扰动理论使用电子结构的密度泛函描述得出了吸附在Si(100)-2 x 1上的1,3-环己二烯(CHD)的[4 + 2]二聚体内加成物的空态STM图像。似乎捕获了实验观察到的π〜* C = C轨道,但最终产生了以CH2基团为主的图像。在有限温度结构上的平均值或在顶点上吸附O或Si的W(110)吸头均不能产生正确的图像。强的尖端-CHD相互作用相对于费米能量而言,大大降低了π〜*轨道的能量,并改变了CHD的几何形状。除了干扰C = C键外,还发现尖端将CH2基团推开。前者的电子效应增强了π〜*轨道的突出性,而后者的几何效应抑制了CHD其余部分的贡献。
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