Composite boson many-body theory for Frenkel excitons

TL;DR

This paper develops a comprehensive many-body theory for Frenkel excitons, accurately accounting for their composite nature and revealing unique transfer-assisted exchange scattering processes crucial for understanding their many-body physics.

Contribution

It introduces a novel many-body framework for Frenkel excitons using commutators and identifies a unique transfer-assisted exchange scattering process.

Findings

Frenkel excitons exhibit a unique transfer-assisted exchange scattering.

Indirect Coulomb processes are essential for excitation transfer in Frenkel excitons.

Frenkel excitons are confirmed to be composite objects despite their localized nature.

Abstract

We present a many-body theory for Frenkel excitons which takes into account their composite nature exactly. Our approach is based on four commutators similar to the ones we previously proposed for Wannier excitons. They allow us to calculate any physical quantity dealing with $N$ excitons in terms of "Pauli scatterings" for carrier exchange in the absence of carrier interaction and "interaction scatterings" for carrier interaction in the absence of carrier exchange. We show that Frenkel excitons have a novel "transfer assisted exchange scattering", specific to these excitons. It comes from indirect Coulomb processes between localized atomic states. These indirect processes, commonly called "electron-hole exchange" in the case of Wannier excitons and most often neglected, are crucial for Frenkel excitons, as they are the only ones responsible for the excitation transfer. We also show that in spite of the fact that Frenkel excitons are made of electrons and holes on the same atomic site, so that we could naively see them as elementary particles, they definitely are composite objects, their composite nature appearing through various properties, not always easy to guess. The present many-body theory for Frenkel excitons is thus going to appear as highly valuable to securely tackle their many-body physics, as in the case of nonlinear optical effects in organic semiconductors.