Optical excitations in nanographenes from the Bethe-Salpeter equation and time-dependent density functional theory: absorption spectra and spatial descriptors

TL;DR

This paper implements and validates the GW-BSE method in the CP2K code to accurately compute optical excitations and spectra of nanographenes, highlighting the importance of many-body approaches over TDDFT.

Contribution

The authors develop and validate a GW-BSE implementation in CP2K for nanostructures, providing accurate optical spectra and excitation sizes, and compare it with TDDFT methods.

Findings

GW-BSE achieves <3 meV error in excitation energies

Optical spectra of nanographenes match experimental data

TDDFT fails to reproduce excitation size and spectra accurately

Abstract

The GW plus Bethe-Salpeter equation (GW-BSE) formalism is a well-established approach for calculating excitation energies and optical spectra of molecules, nanostructures, and crystalline materials. We implement GW-BSE in the CP2K code and validate the implementation for a standard organic molecular test set, obtaining excellent agreement with reference data, with a mean absolute error in excitation energies below 3 meV. We then study optical spectra of nanographenes of increasing length, showing excellent agreement with experiment. We further compute the size of the excitation of the lowest optically active excitation which converges to about 7.6 $\r{A}$ with increasing length. Comparison with time-dependent density functional theory using functionals of varying exact-exchange fraction shows that none reproduce both the size of the excitation and optical spectra of GW-BSE, underscoring the need for many-body methods for accurate description of electronic excitations in nanostructures.