Exciton dispersion in molecular solids

J Phys Condens Matter. 2015 Mar 25;27(11):113204. doi: 10.1088/0953-8984/27/11/113204. Epub 2015 Mar 4.

Abstract

The investigation of the exciton dispersion (i.e. the exciton energy dependence as a function of the momentum carried by the electron-hole pair) is a powerful approach to identify the exciton character, ranging from the strongly localised Frenkel to the delocalised Wannier-Mott limiting cases. We illustrate this possibility at the example of four prototypical molecular solids (picene, pentacene, tetracene and coronene) on the basis of the parameter-free solution of the many-body Bethe-Salpeter equation. We discuss the mixing between Frenkel and charge-transfer excitons and the origin of their Davydov splitting in the framework of many-body perturbation theory and establish a link with model approaches based on molecular states. Finally, we show how the interplay between the electronic band dispersion and the exchange electron-hole interaction plays a fundamental role in setting the nature of the exciton. This analysis has a general validity holding also for other systems in which the electron wavefunctions are strongly localized, as in strongly correlated insulators.

Publication types

  • Research Support, Non-U.S. Gov't
  • Review

MeSH terms

  • Absorption, Physicochemical
  • Electrons*
  • Models, Molecular
  • Optical Phenomena
  • Polycyclic Compounds / chemistry*
  • Quantum Theory

Substances

  • Polycyclic Compounds