Electronic structure tuning of diamondoids through functionalization.
Electronic structure tuning of diamondoids through functionalization.
复制标题
DOI：
10.1063/1.4774268
复制
发表时间：
2013-01
期刊：
影响因子：
--
通讯作者：
T. Rander;M. Staiger;R. Richter;T. Zimmermann;L. Landt;D. Wolter;J. Dahl;R. Carlson;B. Tkachenko;N. Fokina;P. Schreiner;T. Möller;C. Bostedt
中科院分区：
文献类型：
--
作者：
T. Rander;M. Staiger;R. Richter;T. Zimmermann;L. Landt;D. Wolter;J. Dahl;R. Carlson;B. Tkachenko;N. Fokina;P. Schreiner;T. Möller;C. Bostedt
我们研究了五个最小的类金刚石的化学功能化引起的电子结构的变化，使用价光电子能谱。通过三个参数的变化，即官能团（硫醇，羟基和氨基），主机集群大小（金刚烷，金刚烷，三金刚烷，[121]四金刚烷，和[1（2，3）4]五金刚烷），和功能化位点（顶端和中间），我们能够确定在多大程度上这些影响整个系统的电子结构。我们表明，不像，例如，在卤代苯的情况下，电离势不显示线性依赖于官能团的电负性。相反，HOMO-1电离势和官能团电负性之间存在线性相关性。这是由于HOMO在官能团上的定位和HOMO-1在金刚烷笼上的定位。密度泛函理论支持我们的解释。
We investigated the changes in electronic structures induced by chemical functionalization of the five smallest diamondoids using valence photoelectron spectroscopy. Through the variation of three parameters, namely functional group (thiol, hydroxy, and amino), host cluster size (adamantane, diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane), and functionalization site (apical and medial) we are able to determine to what degree these affect the electronic structures of the overall systems. We show that unlike, for example, in the case of halobenzenes, the ionization potential does not show a linear dependence on the electronegativity of the functional group. Instead, a linear correlation exists between the HOMO-1 ionization potential and the functional group electronegativity. This is due to localization of the HOMO on the functional group and the HOMO-1 on the diamondoid cage. Density functional theory supports our interpretations.