Identification of excitons in conjugated polymers: a density matrix renormalisation group study

TL;DR

This study uses advanced computational methods to analyze excitations in conjugated polymers, revealing that common criteria like the charge gap are unreliable for identifying bound excitons, and clarifying the nature of low-lying excited states.

Contribution

It applies the density matrix renormalisation group method to accurately characterize excitations and challenges traditional criteria for exciton binding in conjugated polymers.

Findings

Charge gap is not a reliable indicator of bound excitons.

The mAg state indicates the onset of unbound excitations in the Ag sector.

All low-lying states in the Bu sector are unbound, with no well-defined nBu state.

Abstract

This work addresses the question of whether low-lying excitations in conjugated polymers are comprised of free charge-carriers or excitons. States are characterised as bound or unbound according to the scaling of the average particle-hole separation with system size. We critically examine other criteria commonly used to characterise states. The polymer is described by an extended Hubbard model with alternating transfer integrals. The model is solved by exact diagonalisation and the density matrix renormalisation group (DMRG) method. We demonstrate that the DMRG accurately determines excitation energies, transition dipole moments and particle-hole separations of a number of dipole forbidden (Ag) and dipole allowed (Bu) states. Within a parameter regime considered reasonable for polymers such as polyacetylene, it is found that the charge gap, often used to define the exciton binding energy, is not a good criterion by which to decide whether a state is bound or unbound. The essential non-linear optical state mAg is found to mark the onset of unbound excitations in the Ag symmetry sector. In the Bu symmetry sector, on the other hand, it is found that all low lying states are unbound and that there is no well defined nBu state. That is, the 1Bu state marks the onset of unbound excitations in this sector.