Determination of onset temperature from the entropy for fragile to strong liquids

Banerjee, Atreyee; Nandi, Manoj Kumar; Sastry, Srikanth; Bhattacharyya, S. K.

doi:10.1063/1.4991848

Cited by 35 publications

(39 citation statements)

References 71 publications

(103 reference statements)

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“…On the other side, a close correspondence between the sign crossover of the RMPE and structural or thermodynamical transition thresholds has been highlighted in both two and three dimensions on a variety of model systems for different macroscopic ordering phenomena other than freezing [ 13 ], including fluid demixing [ 14 ], the emergence of mesophases in liquid crystals [ 15 ], the formation of a hydrogen-bonded network in water [ 16 ], or, more recently, the onset of glassy dynamics [ 17 ].…”

Section: Introductionmentioning

confidence: 99%

Residual Multiparticle Entropy for a Fractal Fluid of Hard Spheres

Santos¹,

Saija²,

Giaquinta³

2018

Entropy

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Abstract:The residual multiparticle entropy (RMPE) of a fluid is defined as the difference, ∆s, between the excess entropy per particle (relative to an ideal gas with the same temperature and density), s ex , and the pair-correlation contribution, s 2 . Thus, the RMPE represents the net contribution to s ex due to spatial correlations involving three, four, or more particles. A heuristic "ordering" criterion identifies the vanishing of the RMPE as an underlying signature of an impending structural or thermodynamic transition of the system from a less ordered to a more spatially organized condition (freezing is a typical example). Regardless of this, the knowledge of the RMPE is important to assess the impact of non-pair multiparticle correlations on the entropy of the fluid. Recently, an accurate and simple proposal for the thermodynamic and structural properties of a hard-sphere fluid in fractional dimension 1 < d < 3 has been proposed (Santos, A.; López de Haro, M. Phys. Rev. E 2016, 93, 062126). The aim of this work is to use this approach to evaluate the RMPE as a function of both d and the packing fraction φ. It is observed that, for any given dimensionality d, the RMPE takes negative values for small densities, reaches a negative minimum ∆s min at a packing fraction φ min , and then rapidly increases, becoming positive beyond a certain packing fraction φ 0 . Interestingly, while both φ min and φ 0 monotonically decrease as dimensionality increases, the value of ∆s min exhibits a nonmonotonic behavior, reaching an absolute minimum at a fractional dimensionality d 2.38. A plot of the scaled RMPE ∆s/|∆s min | shows a quasiuniversal behavior in the region −0.14 φ − φ 0 0.02.

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Section: Introductionmentioning

confidence: 99%

Residual Multiparticle Entropy for a Fractal Fluid of Hard Spheres

Santos¹,

Saija²,

Giaquinta³

2018

Entropy

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“…The Stokes-Einstein (SE) relation connects the diffusion coefficient D of a large particle immersed in a solvent with viscosity η, predicting that D ∝ η −1 T. The SE relation breaks down in the supercooled regime and explanations have been presented from various theoretical perspectives 33,38,[63][64][65][66][67][68][69][70] . Flenner et al 68 obtained a good collapse of the diffusion coefficient plotted against the structural relaxation time (which may be used as a proxy for the viscosity) for supercooled binary mixtures by scaling the diffusion coefficient and the relaxation time.…”

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confidence: 99%

Excess-entropy scaling in supercooled binary mixtures

2020

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Transport coefficients, such as viscosity or diffusion coefficient, show significant dependence on density or temperature near the glass transition. Although several theories have been proposed for explaining this dynamical slowdown, the origin remains to date elusive. We apply here an excess-entropy scaling strategy using molecular dynamics computer simulations and find a quasiuniversal, almost composition-independent, relation for binary mixtures, extending eight orders of magnitude in viscosity or diffusion coefficient. Metallic alloys are also well captured by this relation. The excess-entropy scaling predicts a quasiuniversal breakdown of the Stokes-Einstein relation between viscosity and diffusion coefficient in the supercooled regime. Additionally, we find evidence that quasiuniversality extends beyond binary mixtures, and that the origin is difficult to explain using existing arguments for singlecomponent quasiuniversality.

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“…5). Our study reveals that unlike in KA model where there is a clear separation of major contribution to high temperature MCT like dynamics and low temperature activated dynamics from the pair and higher order terms of the entropy respectively 16,33,35,36 , in GCM that separation does not exist. We plot the S ex and S 2 for both KA and GC models as a function of temperature and observe certain stark differences between them.…”

Section: A Excess Entropymentioning

confidence: 53%

Analysis of the anomalous mean-field like properties of Gaussian core model in terms of entropy

Nandi

Bhattacharyya

2018

The Journal of Chemical Physics

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Studies of the Gaussian core model (GCM) have shown that it behaves like a mean-field model and the properties are quite different from standard glass former. In this work, we investigate the entropies, namely the excess entropy (S ex ) and the configurational entropy (S c ) and their different components to address these anomalies. Our study corroborates most of the earlier observations and also sheds new light on the high and low temperature dynamics. We find that unlike in standard glass former where high temperature dynamics is dominated by two-body correlation and low temperature by many-body correlations, in GCM both high and low temperature dynamics are dominated by many body correlations. We also find that the many-body entropy which is usually positive at low temperatures and is associated with activated dynamics is negative in GCM suggesting suppression of activation. Interestingly despite suppression of activation the Adam-Gibbs (AG) relation which describes activated dynamics holds in GCM, thus suggesting a non-activated contribution in AG relation. We also find an overlap between the AG and mode coupling power law regime leading to a power law behaviour of S c . From our analysis of this power law behaviour we predict that in GCM the high temperature dynamics will disappear at dynamical transition temperature and below that, there will be a transition to the activated regime. Our study further reveals that the activated regime in GCM is quite narrow.

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Determination of onset temperature from the entropy for fragile to strong liquids

Cited by 35 publications

References 71 publications

Residual Multiparticle Entropy for a Fractal Fluid of Hard Spheres

Residual Multiparticle Entropy for a Fractal Fluid of Hard Spheres

Excess-entropy scaling in supercooled binary mixtures

Analysis of the anomalous mean-field like properties of Gaussian core model in terms of entropy

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