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Evidence of dynamic crossover phenomena in water and other glass-forming liquids: experiments, MD simulations and theory

S H Chen1,5, Y Zhang1, M Lagi1,2, S H Chong3, P Baglioni2 and F Mallamace4

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In a recent quasi-elastic neutron scattering experiment on water confined in a Portland cement paste, we find that this 3D confined water shows a dynamic crossover phenomenon at TL = 227 ± 5 K. The DSC heat-flow scan upon cooling and an independent measurement of specific heat at constant pressure of confined water in silica gel show a prominent peak at the same temperature. We show in this paper that this type of behavior is common to many other glassy liquids, which also show the crossover temperature in coincidence with the temperature of a small specific heat peak. We also demonstrate with MD simulations that the dynamic crossover phenomenon in confined water is an intrinsic property of bulk water, and is not due to the confinement effect. Recently, an extended version of the mode coupling theory (MCT) including the hopping effect was developed. This theory shows that, instead of a structural arrest transition at TC predicted by the idealized MCT, a fragile-to-strong dynamic crossover phenomenon takes place instead at TC, confirming both the experimental and the numerical results. The coherent and incoherent α relaxation times can be scaled with the calculated viscosity, showing the same crossover phenomenon. We thus demonstrated with experiments, simulations and theory that a genuine change of dynamical behavior of both water and many glassy liquids happens at the crossover temperature TL, which is 10–30% higher than the calorimetric glass transition temperature Tg.


PACS

65.20.-w Thermal properties of liquids

66.20.-d Viscosity of liquids; diffusive momentum transport

64.70.Ja Liquid-liquid transitions

61.20.Ja Computer simulation of liquid structure

82.70.Gg Gels and sols

Subjects

Soft matter, liquids and polymers

Condensed matter: structural, mechanical & thermal

Chemical physics and physical chemistry

Dates

Issue 50 (16 December 2009)

Received 22 April 2009, in final form 28 May 2009

Published 23 November 2009



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