On the limitation of density functional theory (DFT) for the treatment of the anharmonicity in FCC metals

Abstract

Abstract It has been already shown that the density functional theory (DFT) combined with the quasi-harmonic approximation (QHA) overestimates the specific heat capacity (and in general the thermal properties) of fcc metals. DFT + QHA seemingly shows a large anharmonic contribution to the heat capacity. However, in this article we show that this anharmonicity has no physical origin and it is a consequence of the deviation of the QHA from the Maxwell relations. We show that one can simply avoid this overestimation by enforcing the QHA method to obey the Maxwell relations throughout the thermodynamically self-consistent (TSC) method, instead of considering non-real local anharmonic effects.