# Order-disorder transition in $p$-oligophenyls

## TL;DR

This study systematically investigates the order-disorder transitions in p-oligophenyls, revealing how transition temperatures increase with chain length and establishing a phase diagram for these transitions and melting points.

## Contribution

It provides the first detailed analysis of vibrational properties and transition temperatures across different chain lengths of p-oligophenyls, filling a gap in understanding their phase behavior.

## Key findings

- Order-disorder transition temperature increases with chain length.
- Transition temperature saturates around 350 K for poly(para-phenylene).
- Established phase diagram for transition and melting curves.

## Abstract

Poly($para$-phenylene) has been recognized as one important family of conducting polymers upon doping with donors or acceptors. This system possesses a chain-like structure with infinite benzene rings linked with the single C-C bond. Oligophenyls as models of poly($para$-phenylene) with short chains in the \emph{para} position were found to exhibit superconductivity at transition temperatures ranging from 3 K to 123 K upon dopant. Structural studies have revealed that there exist the order-disorder transitions in many \emph{p}-oligophenyls with almost doubled lattice constants in the \emph{b} and \emph{c} directions at low temperatures, seemingly supporting the formation of the charge-density-wave order. Such a transition is of relevance to the understanding of the emergence of novel quantum functionality where unconventional polaronic interactions are relevant for the new emerging theory of superconductivity in this system. However, the accurate temperatures for the order-disorder transitions amongst these \emph{p}-oligophenyls are still needed to be determined. The chain length effects on the order-disorder transitions in this system remain unknown. Here we report the systematic investigation of the evolution of vibrational properties of the crystalline \emph{p}-oligophenyls over a wide temperature range. The order-disorder transition is identified by three indicators, the lowest energy peak together with the intensity ratios between the 1280 cm$^{-1}$ and 1220 cm$^{-1}$ modes and between the two modes at around 1600 cm$^{-1}$. A phase diagram of the order-disorder transition temperature as well as the melting curve for \emph{p}-oligophenyls is thus established. The former is found to increase with the chain length and saturates at around 350 K for poly($para$-phenylene).