Monte Carlo Simulations of the Chemical Potential and Free Energy for Trimer and Hexamer Rings

Abstract

The chemical potential of a trimer and hexamer model ring system was determined by computer simulation over a range of temperatures and densities. Such ring molecules are important as model aromatic and naphthenic hydrocarbons. Thermodynamic integration of the pressure along a reversible path, Widom's ghost particle insertion method and Kirkwood's charging parameter method were used over a molecular density range of 0.05 to 0.30. Data were obtained by Monte Carlo simulation of a 96 molecule system that was modelled with a Lennard-Jones 6-12 truncated potential. The original insertion method, which does not take into account the orientation of the molecule when it is inserted, gives results for the chemical potential which deviate from that obtained using the thermodynamic pressure integration. At high density or temperature the deviation is significant. We have modified the Widom insertion technique to account for this short range orientation and find good agreement between this technique and the thermodynamic integration method for the chemical potential. We also calculated the free energy difference between our model ring molecules and ring molecules made up of hard spheres.

Key Words:

• Chemical potential
• ring systems
• Monte Carlo simulation