Analysis of the effect of the translational-rotational coupling on the pseudo-diffusion along the molecular axes of meta-cresol: A molecular dynamics analysis

Abstract

We investigate the dynamical properties (translation and rotation) of the glass-forming liquid meta-cresol by molecular dynamics simulations. This system is investigated at 9 temperatures between 230 K and 400 K, encompassing the liquid and glassy states of meta-cresol. In order to get insight into the coupling between the translational and rotational motions, the centre of mass velocity autocorrelation function is calculated along the principal axes of meta-cresol. We show that the time behaviour of the velocity and angular velocity is connected to the change in the local structure occurring upon the glass transition. Indeed, the long-time negative region in the velocity autocorrelations is associated with a caging effect while the occurrence of a short time negative region in these functions is considered as a signature of hydrogen bonding interactions. By studying, the centre of mass velocity of meta-cresol in the molecular frame, the translation and rotation coupling was directly evidenced. The time evolution of the translational-rotational coupling is evaluated from the difference ΔαRTC(t) between the velocity autocorrelation function calculated with respect to the molecular frame (where α stands for the three axes of the local cartesian frame fixed to the individual molecule, x, y, and z) of the meta-cresol molecule and that of the same function calculated in the frame of the hypothesis that there is no statistical correlation between the translational and rotational motions. The positive regions of ΔαRTC(t) indicate an occurrence of a cooperative effect, which means that the each of the two motions is realized in the favour of the other. Conversely, negative regions indicate that the rotation and translation motions are anti-cooperative. Our results show that a strong coupling between translation and rotation occurs along the × axis that is perpendicular to the ring of meta-cresol molecule, and also along which the hydrogen bond is established.