Phase behavior of C60 by computer simulation using ab-initio interaction potential

• Published in: International journal of quantum chemistry 2001, Vol.84 (3), p.375-387
• Main Authors: Fartaria, Rui P. S., Silva Fernandes, Fernando M. S., Freitas, Filomena F. M., Rodrigues, Pedro C. R.
• Format: Article
• Language: English
• Subjects: C60; fullerenes; Gibbs ensemble Monte Carlo; Gibbs-Duhem integration; phase diagram
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.1081

A first‐principles intermolecular potential recently proposed by Pacheco and Ramalho [Phys Rev Lett 1997, 79, 3873–3876] has been used with the Gibbs ensemble and Gibbs–Duhem integration Monte Carlo methods to simulate the vapor–liquid and fluid–solid coexistence properties of C60. The critical properties were calculated by fitting the results to the laws of rectilinear diameters and order parameter scaling. The triple‐point properties were determined from the limiting behavior of the Gibbs ensemble vapor–liquid simulations at the lowest temperature range. A stable liquid phase is predicted for temperatures between 1570±20 and 2006±27 K and densities between 0.444±0.003 and 1.05±0.01 nm−3. The estimated critical and triple‐point pressures are, respectively, 35±6 and 5±16 bars. We show for the first time, to our knowledge, that it is possible, strictly by computer simulation, to estimate a triple point for C60 in accordance with the predictions of theoretical methods and the basic concepts of thermodynamics. The liquid and fluid radial distribution functions indicate the presence of solid or glasslike features. This may support the suggestion of a more cooperative interaction of clusters in C60. A comparison of our results with the data obtained by other authors is presented and discussed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 375–387, 2001