First-principles GW-BSE excitations in organic molecules

TL;DR

This paper introduces a first-principles computational approach combining GW and BSE methods to accurately predict optical excitations in organic molecules, validated on benzene and azobenzene, including photoisomerization processes.

Contribution

The paper develops a novel GW-BSE based method for calculating optical excitations in nanosystems, incorporating dynamical screening effects within a DFT framework.

Findings

Accurately predicts excitation energies for benzene and azobenzene.

Describes azobenzene photoisomerization consistent with multi-configuration calculations.

Demonstrates the method's applicability to complex organic molecules.

Abstract

We present a first-principles method for the calculation of optical excitations in nanosystems. The method is based on solving the Bethe-Salpeter equation (BSE) for neutral excitations. The electron self-energy is evaluated within the GW approximation, with dynamical screening effects described within time-dependent density-functional theory in the adiabatic, local approximation. This method is applied to two systems: the benzene molecule, C$_6$H$_6$, and azobenzene, C$_{12}$H$_{10}$N$_2$. We give a description of the photoisomerization process of azobenzene after an $n-\pi^\star$ excitation, which is consistent with multi-configuration calculations.