Periodic polymers with increasing repetition unit: Energy structure and carrier transfer

TL;DR

This paper investigates the energy structure and charge transfer properties of periodic polymers with increasing repetition units, analyzing how sequence composition influences transfer efficiency and comparing theoretical results with experimental data.

Contribution

It introduces a detailed Tight-Binding model for polymers with variable repetition units, revealing how sequence and structure affect energy spectra and charge transfer rates.

Findings

Homopolymers exhibit the most efficient charge transfer.

Transfer rates can be enhanced significantly by sequence optimization.

Theoretical transfer rates align with experimental observations.

Abstract

We study the energy structure and the transfer of an extra electron or hole along periodic polymers made of $N$ monomers, with a repetition unit made of $P$ monomers, using a Tight-Binding wire model, where a site is a monomer (e.g., in DNA, a base pair), for $P$ even, and deal with two categories of such polymers: made of the same monomer (GC..., GGCC..., etc) and made of different monomers (GA..., GGAA..., etc). We calculate the HOMO and LUMO eigenspectra, density of states and HOMO-LUMO gap and find some limiting properties these categories possess, as $P$ increases. We further examine the properties of the mean over time probability to find the carrier at each monomer. We introduce the weighted mean frequency of each monomer and the total weighted mean frequency of the whole polymer, as a measure of the overall transfer frequency content. We study the pure mean transfer rates. These rates can be increased by many orders of magnitude with appropriate sequence choice. Generally, homopolymers display the most efficient charge transfer. Finally, we compare the pure mean transfer rates with experimental transfer rates obtained by time-resolved spectroscopy.