Estimation of the equilibrium free energy for glasses using the Jarzynski equality.

@article{Vinutha2021EstimationOT,
  title={Estimation of the equilibrium free energy for glasses using the Jarzynski equality.},
  author={H A Vinutha and Daan Frenkel},
  journal={The Journal of chemical physics},
  year={2021},
  volume={154 23},
  pages={
          231101
        }
}
The free energy of glasses cannot be estimated using thermodynamic integration as glasses are intrinsically not in equilibrium. We present numerical simulations showing that, in contrast, plausible free-energy estimates of a Kob-Andersen glass can be obtained using the Jarzynski relation. Using the Jarzynski relation, we also compute the chemical potential difference of the two components of this system and find that, in the glassy regime, the Jarzynski estimate matches well with the… 

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References

SHOWING 1-10 OF 27 REFERENCES
Computing Equilibrium Free Energies Using Non-Equilibrium Molecular Dynamics
TLDR
The Jarzynski identity and the Crooks fluctuation theorem are reviewed and various algorithms building on these relations are surveyed, focusing on statistical efficiency and practical issues arising in their implementation and the analysis of the results.
Supercooled liquids and the glass transition
TLDR
Current theoretical knowledge of the manner in which intermolecular forces give rise to complex behaviour in supercooled liquids and glasses is discussed.
Efficient extraction of free energy profiles from nonequilibrium experiments
TLDR
A systematic derivation of the optimum weight is given, which—in principle—minimizes the statistical errors in the resulting free energy profiles of Helmholtzfree energy profiles obtained in simulations or experiments.
An experimental test of the Jarzynski equality in a mechanical experiment
We have experimentally checked the Jarzynski equality and the Crooks relation (see Jarzynski C., Phys. Rev. Lett., 78 (1997) 2690; Crooks G. E., Phys. Rev. E, 60 (1999) 2721; Jarzynski C., J. Stat.
Configurational entropy measurements in extremely supercooled liquids that break the glass ceiling
TLDR
The colossal gap between experiments and simulations is closed but in silico configurations that have no experimental analog yet are created, and measurements consistently confirm that the steep entropy decrease observed in experiments is also found in simulations, even beyond the experimental glass transition.
Testing mode-coupling theory for a supercooled binary Lennard-Jones mixture I: The van Hove correlation function.
  • Kob, Andersen
  • Mathematics, Physics
    Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics
  • 1995
TLDR
From the investigation of these correlation functions, it is concluded that hopping processes are not important on the time scale of the $\beta$-relaxation for this system and for the temperature range investigated.
Optimum protocol for fast-switching free-energy calculations.
  • P. Geiger, C. Dellago
  • Mathematics, Medicine
    Physical review. E, Statistical, nonlinear, and soft matter physics
  • 2010
TLDR
This analysis shows that the reduction in computational effort achieved by the use of steplike protocols can be considerable and typically occur for parameter ranges in which an application of the Jarzynski equation is impractical due to large statistical errors arising from the exponential work average.
On the efficiency of path sampling methods for the calculation of free energies from non-equilibrium simulations
According to the Jarzynski theorem, equilibrium free energy differences can be calculated from the statistics of work carried out during non-equilibrium transformations. Although exact, this approach
The relationship between fragility, configurational entropy and the potential energy landscape of glass-forming liquids
TLDR
Simulations are used to analyse the relationship between fragility and quantitative measures of the energy landscape for a model liquid whose fragility depends on its bulk density and reveal that fragility depend on changes in the vibrational properties of individual energy minima in addition to their total number and spread in energy.
Dependence of the fragility of a glass former on the softness of interparticle interactions.
TLDR
The kinetic fragility of three model binary mixture glass formers is found to increase with increasing softness of the potential, consistent with previous results for these model systems, but at variance with the thermodynamic fragility, which decreases with increasingsoftness ofthe interactions.
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