Effect of dynamical screening in the Bethe-Salpeter framework: Excitons in crystalline naphthalene

TL;DR

This paper investigates the impact of dynamical screening effects on exciton calculations within the Bethe-Salpeter framework for crystalline naphthalene, revealing a significant correction and proposing an efficient approximation method.

Contribution

It introduces a method to incorporate dynamical screening effects into the Bethe-Salpeter equation and compares different approaches for a complex organic crystal.

Findings

Dynamical screening corrections are about 15% of the exciton binding energy.

The study compares approximate and exact methods for dynamical screening.

An effective screening model is proposed for future complex material calculations.

Abstract

Solving the Bethe-Salpeter equation (BSE) for the optical polarization functions is a first principles means to model optical properties of materials including excitonic effects. One almost ubiquitously used approximation neglects the frequency dependence of the screened electron-hole interaction. This is commonly justified by the large difference in magnitude of electronic plasma frequency and exciton binding energy. We incorporated dynamical effects into the screening of the electron-hole interaction in the BSE using two different approximations as well as exact diagonalization of the exciton Hamiltonian. We compare these approaches for a naphthalene organic crystal, for which the difference between exciton binding energy and plasma frequency is only about a factor of ten. Our results show that in this case, corrections due to dynamical screening are about 15\,\% of the exciton binding energy. We analyze the effect of screening dynamics on optical absorption across the visible spectral range and use our data to establish an \emph{effective} screening model as a computationally efficient approach to approximate dynamical effects in complex materials in the future.