On the Role of Internal Degrees of Freedom in Structural Relaxation of Ring-Tail Structured Liquids Across Temperature Regimes

TL;DR

This study explores how internal molecular flexibility and anisotropic rotation affect the relaxation dynamics of 1-phenylalkanes across different temperature regimes, revealing their diminishing influence in supercooled states.

Contribution

It demonstrates the significant role of internal flexibility and anisotropic rotation in liquid relaxation and how their effects change with temperature, providing a new understanding of molecular dynamics.

Findings

Anisotropic rotations and internal flexibility greatly influence liquid relaxation.

Their effects decrease in supercooled regimes, leading to generic relaxation behavior.

The study offers a method to identify these effects in similar molecular liquids.

Abstract

We investigate how anisotropic molecular rotation and internal molecular flexibility influence liquid dynamics in 1-phenylalkanes. To this end, we combine depolarized dynamic light scattering, nuclear magnetic resonance spectroscopy and molecular dynamics simulations. Our results show that anisotropic rotations and internal molecular flexibility substantially contribute to structural relaxation in the liquid state. However, their influence diminishes on entering the supercooled-liquid regime, where the relaxation behavior develops towards the previously identified generic relaxation shape, likely due to the increasing cooperativity of rotational dynamics. Because 1-phenylalkanes are simple model systems with similarities to many other molecular liquids, this study suggests that effects of anisotropic rotation and internal flexibility are relevant in various liquids with similar molecular complexity, and provides a proof of concept for how these effects can be identified.