Modelling of electronic and vibrational properties of carbon nanostructures

Open Access
Margine, Elena Roxana
Graduate Program:
Doctor of Philosophy
Document Type:
Date of Defense:
February 27, 2007
Committee Members:
  • Peter C Eklund, Committee Member
  • Vincent Henry Crespi, Committee Chair
  • Jorge Osvaldo Sofo, Committee Member
  • Henry C Foley, Committee Member
  • electronic structure
  • nanoporous carbon
  • carbon nanotube
  • phonons
  • doping
The main goals of this dissertation work are the analysis and prediction of the properties of nanoscale carbon materials which hold great potential for nanotechnological applications such as strong conductive composites, field-effect transistors, diodes, rechargeable batteries, etc. Some of these exciting applications are already being actively developed, however their design via trial-and-error experimentation is often difficult and expensive. State-of-the-art simulation methods can be used as a powerful tool to streamline the path to practical implementations. In this thesis I use emph{ab initio} quantum-mechanical calculations to explore the response of nanoscale carbon materials to doping. A brief overview of the theoretical methods and of some basic concepts on carbon nanotubes are given in the first two chapters. In Chapter 3 we study the effect of doping in double-walled carbon nanotubes. These systems can be considered as nanoscale capacitors since they have two conducting (or semi-conducting) shells. The experimental work of our collaborators demonstrated for the first time that such a capacitor can be realized by the adsorption of bromine anions at the surface of the outer tube. Our theoretical analysis of the experimental results revealed that this quantum system, surprisingly, behaves exactly as the classical Faraday cage: the electric charge always resides on the outside surface of the conductor, even when the pristine tubes are not metallic. In Chapter 4 I present our findings on the phonon frequencies' response to electron doping in single-walled carbon nanotubes. It is well established that when graphite is doped with electrons, carbon-carbon bonds lengthen and all vibrational frequencies soften. However, in semiconducting carbon nanotubes, the frequency of one mode {it increases} at low levels of alkali doping. Having carefully modelled the process with {it ab initio} methods we conclude that the unusual behavior of the vibrational mode depends on which electronic states are filled first in a given nanotube and therefore this is a direct manifestation of the quantum confinement of electronic states in quasi-one dimensional nanotubes. In Chapter 5 we analyze the behavior of the nearly free electron states in carbon nanotubes. We demonstrate that the rapid decrease in these states' energy under electron doping occurs not because of their hybridization with valence states of the alkali dopant as previously thought, but due to a universal electrostatic mechanism. We show that the nearly free state, being weakly bound to the tube wall, is extraordinarily labile and distorts dramatically to concentrate in the region of highest positive countercharge. Therefore, by taking advantage of the changes in the surrounding environment, the nearly free states may become occupied at unexpectedly low doping levels and play an important role in the transport properties of electron-doped carbon nanotubes. Experimental results have shown that elemental cesium induces graphitization of nanoporous carbon at very low temperatures. In Chapter 6 we propose a compact representative model of nanoporous carbon constructed fully from $sp^2$-connected atoms. Next, we investigate possible mechanisms of its transformation towards graphitization in the presence of dopants. Our results suggest that in addition to the alkali atoms there must be another chemical agent involved in this intriguing low-temperature transformation.