Complementary approaches to the ab initio calculation of melting properties

• Published in: The Journal of chemical physics 2002-04, Vol.116 (14), p.6170-6177
• Main Authors: Alfè, D., Gillan, M. J., Price, G. D.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1460865

Several research groups have recently reported ab initio calculations of the melting properties of metals based on density functional theory, but there have been unexpectedly large disagreements between results obtained by different approaches. We analyze the relations between the two main approaches, based on calculation of the free energies of solid and liquid and on direct simulation of the two coexisting phases. Although both approaches rely on the use of classical reference systems consisting of parametrized empirical interaction models, we point out that in the free energy approach the final results are independent of the reference system, whereas in the current form of the coexistence approach they depend on it. We present a scheme for correcting the predictions of the coexistence approach for differences between the reference and ab initio systems. To illustrate the practical operation of the scheme, we present calculations of the high-pressure melting properties of iron using the corrected coexistence approach, which agree closely with earlier results from the free energy approach. A quantitative assessment is also given of finite-size errors, which we show can be reduced to a negligible size.