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Title: An investigation of the liquid to glass transition using integral equations for the pair structure of coupled replicae

Extensive numerical solutions of the hypernetted-chain (HNC) and Rogers-Young (RY) integral equations are presented for the pair structure of a system of two coupled replicae (1 and 2) of a “soft-sphere” fluid of atoms interacting via an inverse-12 pair potential. In the limit of vanishing inter-replica coupling ε{sub 12}, both integral equations predict the existence of three branches of solutions: (1) A high temperature liquid branch (L), which extends to a supercooled regime upon cooling when the two replicae are kept at ε{sub 12} = 0 throughout; upon separating the configurational and vibrational contributions to the free energy and entropy of the L branch, the Kauzmann temperature is located where the configurational entropy vanishes. (2) Starting with an initial finite coupling ε{sub 12}, two “glass” branches G{sub 1} and G{sub 2} are found below some critical temperature, which are characterized by a strong remnant spatial inter-replica correlation upon taking the limit ε{sub 12} → 0. Branch G{sub 2} is characterized by an increasing overlap order parameter upon cooling, and may hence be identified with the hypothetical “ideal glass” phase. Branch G{sub 1} exhibits the opposite trend of increasing order parameter upon heating; its free energy lies consistently below that ofmore » the L branch and above that of the G{sub 2} branch. The free energies of the L and G{sub 2} branches are found to intersect at an alleged “random first-order transition” (RFOT) characterized by weak discontinuities of the volume and entropy. The Kauzmann and RFOT temperatures predicted by RY differ significantly from their HNC counterparts.« less
Authors:
 [1] ;  [2] ;  [3]
  1. Université de Lorraine, LCP-A2MC, EA 3469, 1 Bd. François Arago, Metz F-57078 (France)
  2. Université Pierre et Marie Curie, UMR 8234 PHENIX, Paris, France and Department of Chemistry, University of Cambridge, Cambridge CB2 1EW (United Kingdom)
  3. Dipartimento di Fisica, Università di Trieste, Strada Costiera 11, 34151 Grignano, Trieste (Italy)
Publication Date:
OSTI Identifier:
22415324
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 17; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRITICAL TEMPERATURE; ENTROPY; FREE ENERGY; GLASS; HEATING; INTEGRAL EQUATIONS; LIQUIDS; NUMERICAL SOLUTION; SOLUTIONS