2017/08/04 by Christian H. Loach, Graeme J. Ackland · 2 citations
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Thermodynamics and Molecular Structure #Density functional theory #Enthalpy #Function (biology) #High-pressure geophysics and materials #Interatomic potential #Materials science #Molecular dynamics #Phase (matter) #Phase diagram #Phase transition #Physics #Quantum mechanics #Space (punctuation) #Stacking #Thermodynamics #cond-mat.mtrl-sci
paper · pdf · doi:10.1103/physrevlett.119.205701
published as Phys. Rev. Lett. 119, 205701 (2017)
arxiv created 2017/08/04 · openalex publication_date 2017/11/14 · arxiv updated 2017/11/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
It is shown that the enthalpy of any close packed structure for a given element can be characterized as a linear expansion in a set of continuous variables αn, which describe the stacking configuration. This enables us to represent the infinite, discrete set of stacking sequences within a finite, continuous space of the expansion parameters Hn. These Hn determine the stable structure and vary continuously in the thermodynamic space of pressure, temperature, or composition. The continuity of both spaces means that only transformations between stable structures adjacent in the Hn space are possible, giving the model predictive as well as descriptive ability. We calculate the Hn using density functional theory (DFT)and interatomic potentials for a range of materials. Some striking results are found: e.g., the Lennard-Jones potential model has 11 possible stable structures and over 50 phase transitions as a function of cutoff range. The very different phase diagrams of Sc, Tl, Y, and the lanthanides are understood within a single theory. We find that the widely reported 9R-fcc transition is not allowed in equilibrium thermodynamics, and in cases where it has been reported in experiments (Li, Na), we show that DFT theory is also unable to predict it.