Electron correlation effects and two-photon absorption in diamond shaped graphene quantum dots

TL;DR

This study provides theoretical evidence of reversed excited state ordering in diamond-shaped graphene quantum dots due to electron correlation effects, affecting their optical properties and potential in non-linear optical device applications.

Contribution

It demonstrates the onset of strong correlation effects in 2D graphene quantum dots, showing their nonluminescent nature and complex excited state absorption spectra, which was not previously established.

Findings

Reversed excited state ordering appears with increasing size in DQDs.

Excellent agreement between calculated and experimental TPA and PA spectra.

Non-linear optical responses in DQDs are highly intricate with multiple even parity states.

Abstract

In quasi-1D $\pi$-conjugated polymers such as \emph{trans}-polyacetylene and polyenes, electron correlation effects determine the "reversed" excited state ordering in which the lowest two-photon $2A_{g}$ state lies below the lowest one-photon $1B_{u}$ state. In this work, we present conclusive theoretical evidence of reversed excited state ordering in fairly 2D $\pi$-conjugated systems, namely, diamond-shaped graphene quantum dots (DQDs). Our electron correlated calculations show that DQDs begin to exhibit reversed excited ordering with increasing size, in disagreement with independent-particle picture. This signals the onset of strong correlation effects which renders them nonluminescent. Further, we calculate and analyze the two-photon absorption (TPA) spectra as well as photoinduced absorption (PA) spectra of these systems and find excellent agreement with the available experimental results. Our investigations demonstrate that unlike a strictly 1D system like\emph{trans}-polyacetylene, the non-linear and excited state absorptions in DQDs are highly intricate, with several even parity states responsible for strong absorptions. Our results could play an important role in the design of graphene-based non-linear optical devices.