Multiscale modeling of thermomechanical properties of stereoregular polymers

Multiscale coarse-grained (CG) models are expected to play the critical roles in molecular simulations of complex polymers. However, this poses a great challenge for accurately simulating their thermomechanical properties, for which excellent representability and transferability are required for the CG potentials. In this work, virtual sites and elastic network bonds are introduced to improve the structural and volumetric property-based CG models including explicit electrostatic interactions, which is exemplarily applied to the iso- and syndio-tactic poly(methyl methacrylate). A variety of thermomechanical properties of the two stereoregular polymer bulks are reasonably reproduced by the extensive molecular dynamics simulations with the so-parameterized CG potentials. In particular, the attractive nature of electrostatic interactions and tacticity effects on glass transition temperatures (T-g) are well captured. Furthermore, stronger electrostatic interactions lead to higher mass density and bulk modulus, and their effects on Young's modulus, Poisson's ratio, and shear modulus depend upon the chain tacticity. It is also demonstrated that all these elastic constants can be effectively modulated by imposing external electric field. The proposed multiscale scheme can be very valuable to molecular designs of polar polymer materials.

Automated summary

This study introduces virtual sites and elastic network bonds to improve the structural and volumetric property-based multiscale coarse-grained (CG) models. By extensively molecular dynamics simulations, the thermomechanical properties of two stereoregular polymer bulks are reasonably reproduced with the so-parameterized CG potentials, including the attractive nature of electrostatic interactions and the tacticity effects on glass transition temperatures (T-g).