Unraveling the success and failure of mode coupling theory from consideration of entropy

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

doi:10.1063/1.4934986

Cited by 32 publications

(39 citation statements)

References 73 publications

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“…However the density range studied here is much higher, thus, predicting that the Rosenfeld relationship is valid over a wider range of densities. Our study also shows that although at low temperatures the WCA system does not follow any density-temperature scaling 21,35,36 , at high temperatures it shows a master plot. The NTW model on the other hand, although is a model of a simple liquid, is known to show characteristics of ionic melts, to be specific the SiO 2 system 26 .…”

Section: Resultsmentioning

confidence: 61%

“…As mentioned in the introduction, the pair entropy S 2 provides 80% − 90% contribution to the excess entropy 4,15,21 and thus, the Rosenfeld relationship can be written in terms of S 2 which is given by,…”

Section: Resultsmentioning

confidence: 99%

“…It has been used in many recent studies of slow relaxation 21,33 . In this work, we consider only the self-part of the total overlap function (i.e.…”

Section: A Relaxation Timementioning

confidence: 99%

“…Samanta et al have found that the mode coupling diffusion coefficient can be fitted to the Rosenfeld scaling under certain approximations 20 . In a recent study we find that mode coupling theory (MCT) vertex is related to pair excess entropy and higher order MCT calculation in the schematic limit can provide the phenomenological Rosenfeld relation 21 . Thus, the scaling law has been derived using different theories.…”

Section: Introductionmentioning

confidence: 99%

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Validity of the Rosenfeld relationship: A comparative study of the network forming NTW model and other simple liquids

2017

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Abstract. In this paper we explore the validity of the Rosenfeld and the Dzugutov relation for the LennardJones (LJ) system, its repulsive counterpart, the WCA system and a network forming liquid, the NTW model. We find that for all the systems both the relations are valid at high temperature regime with an universal exponent close to 0.8. Similar to that observed for the simple liquids, the LJ and the WCA systems show a breakdown of the scaling laws at the low temperature regime. However for the NTW model, which is a simple liquid, these scaling laws are valid even at lower temperature regime similar to that found for ionic melts. Thus we find that the NTW model has mixed characteristics of simple liquids and ionic melts. Our study further reveals a quantitative relationship between the Rosenfeld and the Arrhenius relations. For strong liquids, the validity of the Rosenfeld relation in the low temperature regime is connected to it following the Arrhenius behaviour in that regime. Finally we explore the role of pair entropy and residual multiparticle entropy in the dynamics as a function of fragility of the systems.

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Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 99%

“…It has been used in many recent studies of slow relaxation 21,33 . In this work, we consider only the self-part of the total overlap function (i.e.…”

Section: A Relaxation Timementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Validity of the Rosenfeld relationship: A comparative study of the network forming NTW model and other simple liquids

2017

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“…4 Thus the crossover temperature from 'normal' to 'slow' dynamics can be treated as a) Electronic mail: mb.sarika@ncl.res.in an onset of slow dynamics 4,9,10 . On further cooling, the system reaches a temperature called mode coupling transition temperature T c , at which the power law behavior of the mode coupling theory (MCT) predicts a divergence of the dynamics 11,12 . Earlier studies have reported that the saddle order nearby extrema of the potential energy surface goes to zero at this temperature [13][14][15][16] , thus connecting a landscape property to the dynamical MCT transition temperature.…”

Section: Introductionmentioning

confidence: 99%

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

Banerjee

Nandi

Sastry

et al. 2017

The Journal of Chemical Physics

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In this paper we establish a connection between the onset temperature of glassy dynamics with the change in the entropy for a wide range of model systems. We identify the crossing temperature of pair and excess entropies as the onset temperature. Below the onset temperature, the residual multiparticle entropy(RMPE), the difference between excess and pair entropies, becomes positive. The positive entropy can be viewed as equivalent to the larger phase space exploration of the system. The new method of onset temperature prediction from entropy is less ambiguous, as it does not depend on any fitting parameter like the existing methods. Our study also reveals the connection between fragility and the degree of breakdown of the Stokes Einstein (SE) relation.

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Connecting diffusion and entropy of bulk water at the single particle level

Saha

Mukherjee

2017

J Chem Sci

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The relation between the dynamic (e.g., diffusion) and thermodynamic (e.g., entropy) properties of water and water-like liquids has been an active area of research for a long time. Although several studies have investigated the diffusivity and entropy for different systems, these studies have probed either the configurational entropy or the excess entropy of the overall system. In this study, we focus on the entropy of water at a single molecule level at different temperatures. We have used a method developed in our group to calculate the translational and rotational entropy of individual water molecules at various temperatures. We find that the single water translational and rotational entropy exhibit a transition at around 240 K. The translational entropy of individual water molecules shows a consistent variation with change in temperature whereas the variation in the case of rotational entropy is much smaller at different temperatures. We have also calculated diffusion coefficients of water molecules at these temperatures. We find that diffusion also shows the well-known fragile to strong crossover transition at around the same temperature where transition in entropy values has been seen. We have calculated both kinetic and thermodynamic fragilities and crossover points using diffusion and single water translational entropy values. Finally, we correlate the diffusion and translational entropy of individual water molecules using an analog of the Adam-Gibbs relation.

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Unraveling the success and failure of mode coupling theory from consideration of entropy

Cited by 32 publications

References 73 publications

Validity of the Rosenfeld relationship: A comparative study of the network forming NTW model and other simple liquids

Validity of the Rosenfeld relationship: A comparative study of the network forming NTW model and other simple liquids

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

Connecting diffusion and entropy of bulk water at the single particle level

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