Correlated Electronic Properties of Some Graphene Nanoribbons: A DMRG Study

TL;DR

This study uses advanced DMRG calculations to analyze the electronic properties of narrow graphene nanoribbons, revealing complex correlated behaviors and properties that differ from simpler tight-binding predictions.

Contribution

It provides highly accurate correlated electronic structure data for GNRs, including predictions of magnetization, spin gaps, and optical properties, advancing understanding beyond existing theories.

Findings

Bulk magnetization predicted for 3-ZGNR.

Large spin gap found in 6-AGNR.

All three GNRs exhibit nonzero charge gaps and semiconducting behavior.

Abstract

The significant electron-electron interactions that characterize the {\pi}-electrons of graphene nanoribbons (GNRs) necessitate going beyond one-electron tight-binding description. Existing theories of electron-electron interactions in GNRs take into account one electron-one hole interactions accurately but miss higher order effects. We report highly accurate density matrix renormalization group (DMRG) calculations of the ground state electronic structure, the relative energies of the lowest one-photon versus two-photon excitations and the charge gaps in three narrow graphene nanoribbons (GNRs) within the correlated Pariser-Parr-Pople model for {\pi}-conjugated systems. We have employed the symmetrized DMRG method to investigate the zigzag nanoribbon 3-ZGNR and two armchair nanoribbons 6-AGNR and 5-AGNR, respectively. We predict bulk magnetization of the ground state of 3-ZGNR, and a large spin gap in 6-AGNR in their respective thermodynamic limits. Nonzero charge gaps and semiconducting behavior, with moderate to large exciting binding energies are found for all three nanoribbons, in contradiction to the prediction of tight-binding theory. The lowest two-photon gap in 3-ZGNR vanishes in the thermodynamic limit, while this gap is smaller than the one-photon gap in 5-AGNR. However, in 6-AGNR the one-photon gap is smaller than the two-photon gap and it is predicted to be fluorescent.