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First Order Phase Transition in Liquid Ag to the Heterogeneous G-Phase

An, Qi and Johnson, William L. and Samwer, Konrad and Corona, Sydney L. and Goddard, William A., III (2020) First Order Phase Transition in Liquid Ag to the Heterogeneous G-Phase. Journal of Physical Chemistry Letters, 11 (3). pp. 632-645. ISSN 1948-7185. doi:10.1021/acs.jpclett.9b03699.

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[img] PDF (Simulation details, HA index of the G-phase and liquid, melting temperature of the crystal Ag from two-phase simulation, extended RDF and structure factor analysis on X-, L-, and G-phases, statistics simulations at various temperatures, and Ag glass...) - Supplemental Material
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A molten metal is an atomic liquid that lacks directional bonding and is free from chemical ordering effects. Experimentally, liquid metals can be undercooled by up to ∼20% of their melting temperature but crystallize rapidly in subnanosecond time scales at deeper undercooling. To address this limited metastability with respect to crystallization, we employed molecular dynamics simulations to study the thermodynamics and kinetics of the glass transition and crystallization in deeply undercooled liquid Ag. We present direct evidence that undercooled liquid Ag undergoes a first-order configurational freezing transition from the high-temperature homogeneous disordered liquid phase (L) to a metastable, heterogeneous, configurationally ordered state that displays elastic rigidity with a persistent and finite shear modulus, μ. We designate this ordered state as the G-phase and conclude it is a metastable non-crystalline phase. We show that the L–G transition occurs by nucleation of the G-phase from the L-phase. Both the L- and G-phases are metastable because both ultimately crystallize. The observed first-order transition is reversible: the G-phase displays a first-order melting transition to the L-phase at a coexistence temperature, T_(G,M). We develop a thermodynamic description of the two phases and their coexistence boundary.

Item Type:Article
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URLURL TypeDescription
An, Qi0000-0003-4838-6232
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2020 American Chemical Society. Received: December 13, 2019; Accepted: January 4, 2020; Published: January 4, 2020. Q.A. is supported by the U.S. Nuclear Regulatory Commission (NRC) under Grant No. NRC-HQ-84-15-G-0028. W.L.J and S.C. are supported by NSF Grant Award Number DMR 1710744. K.S. is supported by the DFG, Grant Sa337/10. W.A.G. thanks ONR (N00014-19-1-2081) for support. The authors declare no competing financial interest.
Funding AgencyGrant Number
Nuclear Regulatory CommissionNRCHQ-84-15-G-0028
Deutsche Forschungsgemeinschaft (DFG)Sa337/10
Office of Naval Research (ONR)N00014-19-1-2081
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Issue or Number:3
Record Number:CaltechAUTHORS:20200106-083617159
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Official Citation:First-Order Phase Transition in Liquid Ag to the Heterogeneous G-Phase. Qi An, William L. Johnson, Konrad Samwer, Sydney L. Corona, and William A. Goddard, III. The Journal of Physical Chemistry Letters 2020 11 (3), 632-645 DOI: 10.1021/acs.jpclett.9b03699
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:100524
Deposited By: Tony Diaz
Deposited On:07 Jan 2020 19:40
Last Modified:16 Nov 2021 17:54

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