Electronic Properties of Graphene Nano-Parallelograms: A Thermally Assisted Occupation DFT Computational Study

Abstract

In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally assisted occupation density functional theory (TAO-DFT). Our calculations revealed a monotonic decrease in the singlet–triplet energy gap as the GNP length increased. The GNPs possessed singlet ground states for all the cases examined. With the increase of GNP length, the vertical ionization potential and fundamental gap decreased monotonically, while the vertical electron affinity increased monotonically. Some of the GNPs studied were found to possess fundamental gaps in the range of 1–3 eV, lying in the ideal region relevant to solar energy applications. Besides, as the GNP length increased, the symmetrized von Neumann entropy increased monotonically, denoting an increase in the degree of the multi-reference character associated with the ground state GNPs. The occupation numbers and real-space representation of active orbitals indicated that there was a transition from the nonradical nature of the shorter GNPs to the increasing polyradical nature of the longer GNPs. In addition, the edge/corner localization of the active orbitals was found for the wider and longer GNPs.

Keywords

• TAO-DFT
• electronic properties
• graphene nano-parallelograms
• multi-reference character