The Relative Thermodynamic Stability of Diamond and Graphite

摘要

Recent density-functional theory (DFT) calculations raised the possibility that diamond could be degenerate with graphite at very low temperatures. Through high-accuracy calorimetric experiments closing gaps in available data, we reinvestigate the relative thermodynamic stability of diamond and graphite. For T400 K, graphite is always more stable than diamond at ambient pressure. At low temperatures, the stability is enthalpically driven, and entropy terms add to the stability at higher temperatures. We also carried out DFT calculations: B86bPBE-25X-XDM//B86bPBE-XDM and PBE0-XDM//PBE-XDM results overlap with the experimental -T Delta S results and bracket the experimental values of Delta H and Delta G, displaced by only about 2x the experimental uncertainty. Revised values of the standard thermodynamic functions for diamond are Delta H-f(o)=-2150 +/- 150 J mol(-1), Delta S-f(o)=3.44 +/- 0.03 J K-1 mol(-1) and Delta(f)G(o)=-3170 +/- 150 J mol(-1).