The role of attractive forces in viscous liquids

Berthier, Ludovic; Tarjus, Gilles

doi:doi:10.1063/1.3592709

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Acceleration of the effect of solute on the entropy-volume cross fluctuation density in aqueous 2-butoxyethanol, 1-propanol, and glycerol: The fourth derivative of Gibbs energy

Using a differential pressure perturbation calorimetry developed by us recently [K. Yoshida, S. Baluja, A. Inaba, K. Tozaki, and Y. Koga, “Experimental determination of third derivative of G (III): Differential pressure perturbation calorimetry (II),” J. Solution Chem. (in press)], we experimentally determined the partial molar S–V cross fluctuation density of solute B, SVδB , in binary aqueous solutions for B = 1-propanol (1P) and glycerol (Gly). This third derivative of G provides information ...

Vibrational relaxation of azide ions in liquid-to-supercritical water

The dynamics of vibrational energy relaxation (VER) of the aqueous azide anion was studied over a wide temperature (300 K ≤ T ≤ 663 K) and density (0.6 g cm−3 ≤ ρ ≤ 1.0 g cm−3) range thereby covering the liquid and the supercritical phase of the water solvent. Femtosecond mid-infrared spectroscopy on the ν3 band associated with the asymmetric stretching vibration of the azide anion was used to monitor the relaxation dynamics in a time-resolved fashion. The variation of the vibrational relaxation...

We present evidence from computer simulation that the slowdown of relaxation of a standard Lennard-Jones glass-forming liquid and that of its reduction to a model with truncated pair potentials without attractive tails are quantitatively and qualitatively different in the viscous regime. The pair structure of the two models is however very similar. This finding, which appears to contradict the common view that the physics of dense liquids is dominated by the steep repulsive forces between atoms, is characterized in detail, and its consequences are explored. Beyond the role of attractive forces themselves, a key aspect in explaining the differences in the dynamical behavior of the two models is the truncation of the interaction potentials beyond a cutoff at typical interatomic distance. This leads us to question the ability of the jamming scenario to describe the physics of glass-forming liquids and polymers.

Article Outline

INTRODUCTION
MODELS, SIMULATION, AND PHASE DIAGRAM
1. Models
2. Thermodynamics and phase diagram
CONTRASTING THE BEHAVIOR OF THE PAIR STRUCTURE AND OF THE DYNAMICS
1. Pair correlation functions
2. Dynamic correlations and timescales
3. Two-dimensional case and other examples
4. To be, or not to be (perturbative)
ON THE DENSITY SCALING FOR THE RELAXATION TIME
1. Density scaling in supercooled liquids and polymers
2. Empirical data collapse
3. Analogy with power-law repulsive spheres
IS THE ABSENCE OR PRESENCE OF (APPROXIMATE) SCALING DUE TO ATTRACTION OR TO TRUNCATION IN THE POTENTIAL?
GLASS TRANSITION VERSUS JAMMING PHENOMENON
CONCLUSION

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KEYWORDS and PACS

Keywords

Lennard-Jones potential, liquid theory, polymers, viscosity, vitrification

PACS

66.20.Ej

Studies of viscosity and rheological properties of specific liquids
64.70.pj

Polymers
64.70.pm

Liquids
61.20.Ja

Computer simulation of liquid structure
66.20.Cy

Theory and modeling of viscosity and rheological properties, including computer simulation

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http://dx.doi.org/10.1063/1.3592709

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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