The Adam–Gibbs relation and the TIP4P/2005 model of water

Handle, Philip H.; Sciortino, Francesco

doi:10.1080/00268976.2018.1471230

Cited by 18 publications

(11 citation statements)

References 45 publications

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“…In this work, we study the LDA HDA transformation in water using molecular dynamics (MD) simulations in conjunction with the potential energy landscape (PEL) approach [43][44][45][46][47]. The PEL approach is a powerful theoretical framework within statistical mechanics that has been used extensively to study the dynamic and thermodynamic behavior of liquids at low temperatures [48][49][50][51], including water [52][53][54][55]. In particular, it allows one to express the Helmholtz free energy F (N, T, V ) of a liquid [and hence, the corresponding equation of state (EOS)] in terms of statistical properties of the PEL.…”

Section: Introductionmentioning

confidence: 99%

Glass polymorphism in TIP4P/2005 water: A description based on the potential energy landscape formalism

Handle

Sciortino

Giovambattista

2019

The Journal of Chemical Physics

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The potential energy landscape (PEL) formalism is a statistical mechanical approach to describe supercooled liquids and glasses. Here we use the PEL formalism to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) using computer simulations of the TIP4P/2005 molecular model of water. We find that the properties of the PEL sampled by the system during the LDA-HDA transformation exhibit anomalous behavior.In particular, at conditions where the change in density during the LDA-HDA transformation is approximately discontinuous, reminiscent of a first-order phase transition, we find that (i) the inherent structure (IS) energy, eIS(V ), is a concave function of the volume, and (ii) the IS pressure, PIS(V ), exhibits a van der Waals-like loop. In addition, the curvature of the PEL at the IS is anomalous, a non-monotonic function of V . In agreement with previous studies, our work suggests that conditions (i) and (ii) are necessary (but not sufficient) signatures of the PEL for the LDA-HDA transformation to be reminiscent of a first-order phase transition. We also find that one can identify two different regions of the PEL, one associated to LDA and another to HDA. Our computer simulations are performed using a wide range of compression/decompression and cooling rates. In particular, our slowest cooling rate (0.01 K/ns) is within the experimental rates employed in hyperquenching experiments to produce LDA. Interestingly, the LDA-HDA transformation pressure that we obtain at T = 80 K and at different rates extrapolates remarkably well to the corresponding experimental pressure.

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Section: Introductionmentioning

confidence: 99%

Glass polymorphism in TIP4P/2005 water: A description based on the potential energy landscape formalism

Handle

Sciortino

Giovambattista

2019

The Journal of Chemical Physics

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“…The AG theory is founded on arguments related to the concept of cooperatively rearranging regions (CRR), in which the relaxation processes are cooperatively in character. On cooling, the size of the CRR increases, causing the configurational entropy to decrease and the dynamics to slow down [ 54 ]. These CRR can be associated with the so-called dynamic heterogeneities, which are regions of the system characterized by different collective dynamics (with respect to the average) and ascribed to be the imputato for the decoupling between rotational and translational dynamics, expressed as the violation of the Stokes–Einstein relation [ 55 ].…”

Section: Results and Discussionmentioning

confidence: 99%

From Critical Point to Critical Point: The Two-States Model Describes Liquid Water Self-Diffusion from 623 to 126 K

Corsaro

Fazio

2021

Molecules

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Liquid’s behaviour, when close to critical points, is of extreme importance both for fundamental research and industrial applications. A detailed knowledge of the structural–dynamical correlations in their proximity is still today a target to reach. Liquid water anomalies are ascribed to the presence of a second liquid–liquid critical point, which seems to be located in the very deep supercooled regime, even below 200 K and at pressure around 2 kbar. In this work, the thermal behaviour of the self-diffusion coefficient for liquid water is analyzed, in terms of a two-states model, for the first time in a very wide thermal region (126 K < T < 623 K), including those of the two critical points. Further, the corresponding configurational entropy and isobaric-specific heat have been evaluated within the same interval. The two liquid states correspond to high and low-density water local structures that play a primary role on water dynamical behavior over 500 K.

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“…It is truly remarkable how much of the AG theory has survived in the more modern and validated description of GF liquids, which is a testament to the deep physical understanding that AG had of the essential nature of GF liquids. In particular, the AG theory has held up remarkably well over the last 50 years in comparison with numerous experiments 49,140,144,145 and simulations [146][147][148][149][150][151][152][153][154][155][156][157][158][159][160][161][162][163] of diverse GF liquids. Efforts have also been made to place the AG model on a sounder theoretical foundation by extending TST to account for barrier crossing processes that involve many particles, 73,[164][165][166] basically formalizing the heuristic ideas introduced long before Mott and AG.…”

Section: Adam-gibbs Theorymentioning

confidence: 99%

Polymer Glass Formation: Role of Activation Free Energy, Configurational Entropy, and Collective Motion

Xu,

Douglas,

Sun

2021

Preprint

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We provide a perspective on polymer glass formation, with an emphasis on models in which the fluid entropy and collective particle motion dominate the theoretical description and data analysis. The entropy theory of glass formation has its origins in experimental observations relating to correlations between the fluid entropy and liquid dynamics going back nearly a century ago, and it has entered a new phase in recent years. We first discuss the dynamics of liquids in the high temperature Arrhenius regime, where transition state theory is formally applicable. We then summarize the evolution of the entropy theory from a qualitative framework for organizing and interpreting temperature-dependent viscosity data by Kauzmann to the formulation of a hypothetical 'ideal thermodynamic glass transition' by Gibbs and DiMarzio, followed by seminal measurements linking entropy and relaxation by Bestul and Chang and the Adam-Gibbs (AG) model of glass formation rationalizing the observations of Bestul and Chang. These developments laid the groundwork for the generalized entropy theory (GET), which merges an improved lattice model of polymer thermodynamics accounting for molecular structural details and enabling the analytic calculation of the configurational entropy with the AG model, giving rise to a highly predictive model of the segmental structural relaxation time of polymeric glass-forming liquids. The development of the GET has occurred in parallel with the string model of glass formation in which concrete realizations of the cooperatively rearranging regions are identified and quantified for a wide range of polymeric and other glass-forming materials. The string model has shown that many of the assumptions of AG are well supported by simulations, while others are certainly not, giving rise to an entropy theory of glass formation that is largely in accord with the GET. As the GET and string models continue to be refined, these models progressively grow into a more unified framework, and this Perspective reviews the present status of development of this promising approach to the dynamics of polymeric glass-forming liquids.

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The Adam–Gibbs relation and the TIP4P/2005 model of water

Cited by 18 publications

References 45 publications

Glass polymorphism in TIP4P/2005 water: A description based on the potential energy landscape formalism

Glass polymorphism in TIP4P/2005 water: A description based on the potential energy landscape formalism

From Critical Point to Critical Point: The Two-States Model Describes Liquid Water Self-Diffusion from 623 to 126 K

Polymer Glass Formation: Role of Activation Free Energy, Configurational Entropy, and Collective Motion

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