String-Like Collective Atomic Motion in the Melting and Freezing of Nanoparticles

H Zhang and P Kalvapalle and JF Douglas, JOURNAL OF PHYSICAL CHEMISTRY B, 115, 14068-14076 (2011).

DOI: 10.1021/jp203765x

The melting of a solid represents a transition between a solid state in which atoms are localized about fixed average crystal lattice positions to a fluid state that is characterized by relative atomic disorder and particle mobility so that the atoms wander around the material as a whole, impelled by the random thermal impulses of surrounding atoms. Despite the fundamental nature and practical importance of this particle delocalization transition, there is still no fundamental theory of melting and instead one often relies on the semi-phenomenological Lindemann-Gilvarry criterion to estimate roughly the melting point as an instability of the crystal lattice. Even the earliest simulations of melting in hexagonally packed hard discs by Alder and Wainwright indicated the active role of nonlocal collective atomic motions in the melting process, and here we utilize molecular dynamics (MD) simulation to determine whether the collective particle motion observed in melting has a similar geometrical form as those in recent studies of nanoparticle (NP) interfacial dynamics and the molecular dynamics of metastable glass-forming liquids. We indeed find string-like collective atomic motion in NP melting that is remarkably similar in form to the collective interfacial motions in NPs at equilibrium and to the collective motions found in the molecular dynamics of glass-forming liquids. We also find that the spatial localization and extent of string-like motion in the course of NP melting and freezing evolves with time in distinct ways. Specifically, the collective atomic motion propagates from the NP surface and from within the NP in melting and freezing, respectively, and the average string length varies smoothly with time during melting. In contrast, the string-like cooperative motion peaks in an intermediate stage of the freezing process, reflecting a general asymmetry in the dynamics of NP superheating and supercooling.

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