Theoretical description of phase coexistence in model C60

TL;DR

This paper evaluates liquid state theories and perturbation methods against Monte Carlo simulations to accurately describe phase coexistence in the Girifalco C60 model, providing a benchmark for future fullerene studies.

Contribution

It offers a comprehensive assessment of MHNC, SCOZA, and perturbation theories in predicting the phase diagram of C60 fullerenes, validated against recent simulation data.

Findings

All theories reproduce the phase diagram fairly well.

MHNC and SCOZA accurately predict liquid-vapor coexistence.

The combined approach serves as a benchmark for fullerene material modeling.

Abstract

We have investigated the phase diagram of the Girifalco model of C60 fullerene in the framework provided by the MHNC and the SCOZA liquid state theories, and by a Perturbation Theory (PT), for the free energy of the solid phase. We present an extended assessment of such theories as set against a recent Monte Carlo study of the same model [D. Costa et al, J. Chem. Phys. 118:304 (2003)]. We have compared the theoretical predictions with the corresponding simulation results for several thermodynamic properties. Then we have determined the phase diagram of the model, by using either the SCOZA, or the MHNC, or the PT predictions for one of the coexisting phases, and the simulation data for the other phase, in order to separately ascertain the accuracy of each theory. It turns out that the overall appearance of the phase portrait is reproduced fairly well by all theories, with remarkable accuracy as for the melting line and the solid-vapor equilibrium. The MHNC and SCOZA results for the liquid-vapor coexistence, as well as for the corresponding critical points, are quite accurate. All results are discussed in terms of the basic assumptions underlying each theory. We have selected the MHNC for the fluid and the first-order PT for the solid phase, as the most accurate tools to investigate the phase behavior of the model in terms of purely theoretical approaches. The overall results appear as a robust benchmark for further theoretical investigations on higher order C(n>60) fullerenes, as well as on other fullerene-related materials, whose description can be based on a modelization similar to that adopted in this work.