Adhikari Bibek, Fyta Maria
Institute for Computational Physics, University of Stuttgart, Allmandring 3, D-70569 Stuttgart, Germany.
Nanotechnology. 2015 Jan 21;26(3):035701. doi: 10.1088/0957-4484/26/3/035701. Epub 2014 Dec 30.
Diamondoids are nanoscale diamond-like cage structures with hydrogen terminations, which can occur in various sizes and with a diverse type of modifications. In this work, we focus on the structural alterations and the effect of doping and functionalization on the electronic properties of diamondoids, from the smallest adamantane to heptamantane. The results are based on quantum mechanical calculations. We perform a self-consistent study, starting with doping the smallest diamondoid, adamantane. Boron, nitrogen, silicon, oxygen, and phosphorus are chosen as dopants at sites which have been previously optimized and are also consistent with the literature. At a next step, an amine- and a thiol- group are separately used to functionalize the adamantane molecule. We mainly focus on a double functionalization of diamondoids up to heptamantane using both these atomic groups. The effect of isomeration in the case of tetramantane is also studied. We discuss the higher efficiency of a double-functionalization compared to doping or a single-functionalization of diamondoids in tuning the electronic properties, such as the electronic band-gap, of modified small diamondoids in view of their novel nanotechnological applications.
金刚烷类化合物是具有氢端基的纳米级类金刚石笼状结构，其尺寸各异且有多种修饰类型。在这项工作中，我们关注从最小的金刚烷到庚金刚烷的金刚烷类化合物的结构变化以及掺杂和官能化对其电子性质的影响。结果基于量子力学计算。我们进行了一项自洽研究，从对最小的金刚烷类化合物金刚烷进行掺杂开始。选择硼、氮、硅、氧和磷作为掺杂剂，掺杂位点已预先优化且与文献一致。下一步，分别使用胺基和硫醇基对金刚烷分子进行官能化。我们主要关注使用这两种原子基团对直至庚金刚烷的金刚烷类化合物进行双官能化。还研究了四金刚烷异构化的影响。鉴于其新颖的纳米技术应用，我们讨论了与掺杂或单官能化相比，双官能化在调节改性小金刚烷类化合物的电子性质（如电子带隙）方面的更高效率。
