Statistical Mechanics of Glass Formation in Molecular Liquids with OTP as an Example

TL;DR

This paper extends a statistical mechanical theory of the glass transition to molecular liquids with internal degrees of freedom, demonstrating good agreement with simulations for thermodynamic and dynamic properties.

Contribution

It introduces a new approach analyzing local molecular neighborhoods to model glass formation in molecular liquids.

Findings

Good agreement with simulations for thermodynamic properties

Accurate modeling of dynamical behavior in super-cooled liquids

Extension of theory from point particles to complex molecules

Abstract

We extend our statistical mechanical theory of the glass transition from examples consisting of point particles to molecular liquids with internal degrees of freedom. As before, the fundamental assertion is that super-cooled liquids are ergodic, although becoming very viscous at lower temperatures, and are therefore describable in principle by statistical mechanics. The theory is based on analyzing the local neighborhoods of each molecule, and a statistical mechanical weight is assigned to every possible local organization. This results in an approximate theory that is in very good agreement with simulations regarding both thermodynamical and dynamical properties.