Computational study of geometry, electronic structure and low-lying excited states of linear T-graphene quantum dots

Abstract

A few years ago, by means of first-principles calculations, Enyashin et al.(2011) proposed several novel monolayers of carbon containing rings other than hexagons. One of those monolayers containing tetragons and octagons was investigated later in detail by Liu et al.(2012) who called it T-graphene, and found that it exists both in strictly planar and buckled forms, with the planar structure being metallic in nature. Given the fact that Kotakoski et al.(2011) had already found experimental evidence of 1D carbon structures containing tetragons and octagons, we decided to investigate finite linear fragments of T-graphene, with the strictly planar structures, referred to as T-graphene quantum dots (TQDs). In order to avoid the dangling bonds in the finite T-graphene fragments, we considered the edges to be saturated by hydrogen atoms. We first optimized the geometries of the considered TQDs using a first-principles density-functional theory (DFT) methodology, followed by calculations of their linear optical absorption spectra using the time-dependent DFT (TDDFT) approach. Given the fact that strictly planar T-graphene structures will have $\sigma$-$\pi$ separation with the $\pi$ electrons near the Fermi level, we also parameterized an effective $\pi$-electron Hamiltonian for TQDs, similar to the Pariser-Parr-Pople model for $\pi$-conjugated molecules. We further used the effective Hamiltonian to perform high-order electron-correlated calculations using the configuration interaction (CI) approach to compute the optical absorption spectra of TQDs, and also their singlet-triplet gaps. The symmetry analysis reveals that TQDs are photoluminescent materials. Moreover, in all the TQDs HOMO-LUMO transition is optically forbidden, the optical gaps of these molecules are quite large, suggesting the intriguing possibility of the fission of a singlet optical exciton into several triplet excitons.

main manuscript: 40 pages, 10 figures, 5 tables; Supporting information: 16 pages, 2 figures, 16 tables

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