Chemical Control and Spectral Fingerprints of Electronic Coupling in Carbon Nanostructures.
Chemical Control and Spectral Fingerprints of Electronic Coupling in Carbon Nanostructures.
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DOI：
10.1021/acs.jpcc.6b09612
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发表时间：
2016-12-29
期刊：
影响因子：
--
通讯作者：
Wang Y
中科院分区：
文献类型：
--
作者：
Kłos J;Kim M;Alexander MH;Wang Y
单壁碳纳米管和石墨烯等原子级薄材料的光学和电子性质受到基底、聚集程度和化学环境的敏感影响。然而，确定起源和量化这些影响在实验上具有挑战性。在这里，我们使用依赖于时间的密度泛函理论计算来模拟这些性质定义明确的分子系统。我们研究了一系列的核壳结构，包含C60封闭在逐渐变大的碳壳和它们的全氢化或全氟化衍生物。我们的计算揭示了强烈的电子耦合效应，敏感地依赖于粒子间的距离和表面化学。在许多这些系统中，我们预测相当大的轨道混合和电荷转移之间的C60核心和封闭的外壳。我们预测，壳的化学功能化可以调节电子耦合到核和壳完全解耦成两个电子独立的化学系统的点。此外，我们预测，C60核心将振荡的限制壳内，在一个频率直接相关的电子耦合的强度。这种低频运动应该在红外区实验上可以检测到。
The optical and electronic properties of atomically thin materials such as single-walled carbon nanotubes and graphene are sensitively influenced by substrates, the degree of aggregation, and the chemical environment. However, it has been experimentally challenging to determine the origin and quantify these effects. Here we use time-dependent density-functional-theory calculations to simulate these properties for well-defined molecular systems. We investigate a series of core–shell structures containing C60 enclosed in progressively larger carbon shells and their perhydrogenated or perfluorinated derivatives. Our calculations reveal strong electronic coupling effects that depend sensitively on the interparticle distance and on the surface chemistry. In many of these systems we predict considerable orbital mixing and charge transfer between the C60 core and the enclosing shell. We predict that chemical functionalization of the shell can modulate the electronic coupling to the point where the core and shell are completely decoupled into two electronically independent chemical systems. Additionally, we predict that the C60 core will oscillate within the confining shell, at a frequency directly related to the strength of the electronic coupling. This low-frequency motion should be experimentally detectable in the IR region.
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