title: The thermodynamic scale of inorganic crystalline metastability.
abstract: The space of metastable materials offers promising new design opportunities for next-generation technological materials, such as complex oxides, semiconductors, pharmaceuticals, steels, and beyond. Although metastable phases are ubiquitous in both nature and technology, only a heuristic understanding of their underlying thermodynamics exists. We report a large-scale data-mining study of the Materials Project, a high-throughput database of density functional theory-calculated energetics of Inorganic Crystal Structure Database structures, to explicitly quantify the thermodynamic scale of metastability for 29,902 observed inorganic crystalline phases. We reveal the influence of chemistry and composition on the accessible thermodynamic range of crystalline metastability for polymorphic and phase-separating compounds, yielding new physical insights that can guide the design of novel metastable materials. We further assert that not all low-energy metastable compounds can necessarily be synthesized, and propose a principle of 'remnant metastability'-that observable metastable crystalline phases are generally remnants of thermodynamic conditions where they were once the lowest free-energy phase.
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 USA.; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors.forename: Wenhao
authors.initials: W
authors.lastname: Sun
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 USA.
authors.forename: Stephen T
authors.identifier: 0000-0002-7737-1278
authors.initials: ST
authors.lastname: Dacek
authors.affiliation: Department of NanoEngineering, University of California, San Diego, La Jolla, CA 92093, USA.
authors.forename: Shyue Ping
authors.identifier: 0000-0001-5726-2587
authors.initials: SP
authors.lastname: Ong
authors.affiliation: Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Louvain-la-Neuve 1348, Belgium.
authors.forename: Geoffroy
authors.initials: G
authors.lastname: Hautier
authors.affiliation: Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors.forename: Anubhav
authors.initials: A
authors.lastname: Jain
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 USA.
authors.forename: William D
authors.initials: WD
authors.lastname: Richards
authors.affiliation: Computational and Applied Statistics Laboratory, Department of Mathematics, University of California, San Diego, La Jolla, CA 92093, USA.
authors.forename: Anthony C
authors.initials: AC
authors.lastname: Gamst
authors.affiliation: Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.; Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA.
authors.forename: Kristin A
authors.initials: KA
authors.lastname: Persson
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 USA.; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.; Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA.
authors.forename: Gerbrand
authors.initials: G
authors.lastname: Ceder
keywords: DFT; High-throughput Computation; Inorganic Chemistry; Materials Informatics; ab initio thermodynamics; metastability