Thermodynamics, EOS, and heat capacity in molecular modeling of self-assembled molecular layers

Self-assembled monolayers (SAMs) on solid surfaces represent a rapidly developed class of non-autonomous phases widely used in organic electronics, sensors, catalysis, and other applications. In many cases, the same organic molecules form various stable and metastable polymorphous structures that can transform to each other at certain parameters. A high rigidity of SAMs extremely complicates the evaluation of the chemical potential using standard methods based on thermodynamic integration. This study presents results of molecular modeling of two-dimensional structures of tripod-shaped molecules associated with the trimesic acid (TMA) molecules. A technique used here is based on a recently developed method of external fields imposed on an elongated simulation cell in the framework of a kinetic Monte Carlo algorithm. These fields are the external potential and a damping field that reduces the intermolecular potential and affects the system similar to the increase in temperature. Equations of state (EOS) for several TMA polymorphs have been obtained with the conventional Monte Carlo simulation. It was shown that, in each case, only one constant links the chemical potential obtained with the external field method and the EOS at any temperature and pressure. The heat capacities of SAMs at constant volume and pressure were also determined as functions of temperature and compressibility of the structure at given degrees of freedom. The approach can be used as a general tool for modeling and evaluation of thermodynamic properties of various rigid structures, including SAMs of functional organic molecules.