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Research over the past three decades has presented mounting evidence for kinetic pathways of crystal nucleation that are more complex than envisioned by the simplest forms of classical theory. Such observations have been presented for colloidal and elemental systems with covalent and metallic bonding. Despite the technological and geochemical importance of molten salts, similar studies for these ionically bonded systems are currently lacking. Here we develop a machine learning interatomic potential for a model ionic system: LiF. The potential features quantum-level accuracy for both liquid and multiple solid polymorphs over wide temperature and pressure ranges and accurately reproduces experimentally measured properties. Thanks to the efficiency of the potential, which enables microsecond-scale molecular dynamics simulations, induction times for nucleation of LiF solids from their melts are computed over a range of undercoolings. With the aid of a set of robust local order parameters established here, the simulations reveal that homogeneous crystal nucleation in undercooled melts preferentially initiates from liquid regions showing slow dynamics and high bond orientational order simultaneously, and the second-shell order of both precritical nuclei and the surface of postcritical nuclei is dominated by hexagonal close packing and body-centered cubic local structure, even though the nucleus core is dominated by face-centered cubic structure corresponding to the stable rocksalt crystal structure. Finally, we establish a connection between the crystallization pathway and the equilibrium crystal\u2013melt interface structure.<\/jats:p>","DOI":"10.1073\/pnas.2425702122","type":"journal-article","created":{"date-parts":[[2025,6,20]],"date-time":"2025-06-20T14:11:07Z","timestamp":1750428667000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":3,"title":["Multistage nucleation pathway in LiF molten salt mirrors the crystal\u2013melt interface structure"],"prefix":"10.1073","volume":"122","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2523-2532","authenticated-orcid":false,"given":"Zhao","family":"Fan","sequence":"first","affiliation":[{"name":"Materials Sciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]},{"name":"Department of Materials Science and Engineering","place":["Berkeley"]},{"name":"University of California","place":["Berkeley"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0908-519X","authenticated-orcid":false,"given":"Deepak","family":"Rawat","sequence":"additional","affiliation":[{"name":"Materials Sciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Piotr","family":"Zarzycki","sequence":"additional","affiliation":[{"name":"Energy Geosciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael L.","family":"Whittaker","sequence":"additional","affiliation":[{"name":"Materials Sciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]},{"name":"Energy Geosciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8968-321X","authenticated-orcid":false,"given":"Mark","family":"Asta","sequence":"additional","affiliation":[{"name":"Materials Sciences Division","place":["Berkeley"]},{"name":"Lawrence Berkeley National Laboratory","place":["Berkeley"]},{"name":"Department of Materials Science and Engineering","place":["Berkeley"]},{"name":"University of California","place":["Berkeley"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"341","published-online":{"date-parts":[[2025,6,20]]},"reference":[{"key":"e_1_3_4_1_2","volume-title":"Nucleation in Condensed Matter: Applications in Materials and Biology","author":"Kelton K.","year":"2010","unstructured":"K. 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