Internal Secondary Relaxation as a Dielectric Probe of Molecular Surroundings

J Phys Chem Lett. 2024 Mar 7;15(9):2595-2600. doi: 10.1021/acs.jpclett.4c00128. Epub 2024 Feb 28.

Abstract

We investigated the secondary relaxation behavior in rotor molecules in a glassy and crystalline state by using the dielectric method. Without changing the molecular source of secondary relaxation, only by modifying the environment around the rotating unit we observed notable variations in spectral parameters. Our results show that internal rotation, like a probe, can sample the immediate surroundings with high sensitivity to molecular-level changes that impact the rotation parameters. Our research offers a new perspective on the dielectric behavior of internal secondary relaxations and challenges the paradigm of their irrelevant nature.