Isotropic rotation vs. shear relaxation in supercooled liquids with globular cage molecules

The temperature dependence of the rotational dynamics of P4Se3 molecules in the glass-forming molecular liquid P5Se3 is studied using two-dimensional 31P nuclear magnetic resonance spectroscopy. Unlike typical molecular glass-forming liquids, the constituent molecules in the P5Se3 liquid perform rapid isotropic rotation without significant translational diffusion in the supercooled regime and this rotational process shows a decoupling in time scale from shear relaxation by nearly six orders of magnitude at the glass transition. This dynamical behavior of liquid-like rotation and localized translation appears to be universal to glass-forming liquids with high-symmetry globular molecules that are characterized by an underlying thermodynamically stable plastic crystal phase. Published by AIP Publishing.