Polarons as Nucleation Droplets in Non-Degenerate Polymers

TL;DR

This paper investigates how polarons act as nucleation droplets facilitating phase decay in non-degenerate polymers, highlighting the decay mechanisms, energy barriers, and quantum effects relevant at low temperatures.

Contribution

It identifies polarons as critical nucleation droplets in non-degenerate polymers and estimates decay rates and quantum crossover temperatures within a continuum electron-phonon model.

Findings

Decay rate estimates align with experimental gap values.

Activation energies for polarons are approximately 0.1 eV.

Quantum nucleation crossover occurs below 40 K.

Abstract

We present a study of the nucleation mechanism that allows the decay of the metastable phase (trans-cisoid) to the stable phase (cis-transoid) in quasi one-dimensional non-degenerate polymers within the continuum electron-phonon model. The electron-phonon configurations that lead to the decay, i.e. the critical droplets (or transition state), are identified as polarons of the metastable phase. We obtain an estimate for the decay rate via thermal activation within a range of parameters consistent with experimental values for the gap of the cis-configuration. It is pointed out that, upon doping, the activation barriers of the excited states are quite smaller and the decay rate is greatly enhanced. Typical activation energies for electron or hole polarons are $\approx 0.1$ eV and the typical size for a critical droplet (polaron) is about $20 \AA$. Decay via quantum nucleation is also studied and it is found that the crossover temperature between quantum nucleation and thermal activation is of order $T_c \leq 40 ^oK$. Metastable configurations of non-degenerate polymers may provide examples for mesoscopic quantum tunneling.