Shear rate dependence of free energy barrier height for phenyl ring rotations in polystyrene based on non-equilibrium molecular dynamics simulations

Abstract

Polystyrene properties are influenced by ring motions in side groups. The main chain conformation and interaction with the surroundings dominate the ring rotations. It is known that shear flow affects linear chain conformation and molecular distribution. However, shear-induced variations in the ring rotations have yet to be studied. This study presents a shear flow system of polystyrene via non-equilibrium molecular dynamics simulations. The free energy barrier of the phenyl ring rotations was obtained from the distribution of angle χ between the ring and main chain based on the Boltzmann distribution law. The results showed that the barrier height approaches a constant value at a shear rate less than 10¹⁰ s^− 1, but decreases with an increase in shear rate higher than 10^10.5 s^− 1. Furthermore, the radial distribution function and potential energies were compared. Remarkably, the shear flow reduced the bond vibrations of the phenyl rings, but increased the separation between intermolecular particles. Hence, a smaller cavity is necessary for the rings to rotate once but more volume is occupied by the rings. The smaller volume obtained via main chain motions needed to construct the cavity lowers the energy barrier height at shear rate higher than 10^10.5 s^− 1.

Keywords:

• molecular dynamics simulation
• polystyrene
• ring rotations
• shear flow

Acknowledgements

We gratefully acknowledge the financial support from National Science Council of the Republic of China (Grant number: NSC 100-2221-E-007-038) and from CoreTech System Co., Ltd (Moldex3D).

Notes

1 Email: [email protected].

Additional information

Notes on contributors

Wen-Yen Chang

1