Information Entropy of Liquid Metals

Gao, M. C.; Widom, M.

doi:10.1021/acs.jpcb.7b10723

Title: Information Entropy of Liquid Metals

Abstract

Correlations reduce the configurational entropies of liquids below their ideal gas limits. By means of first-principles molecular dynamics simulations, we obtain accurate pair correlation functions of liquid metals, then subtract the mutual information content of these correlations from the ideal gas entropies to predict the absolute entropies over a broad range of temperatures. We apply this method to liquid aluminum and copper and demonstrate good agreement with experimental measurements; then, we apply it to predict the entropy of a liquid aluminum–copper alloy. In conclusion, corrections due to electronic entropy and many-body correlations are discussed.

Authors:

Gao, M. C. ^[1];

^[2]

National Energy Technology Lab. (NETL), Albany, OR (United States); AECOM, Albany, OR (United States)
Carnegie Mellon Univ., Pittsburgh, PA (United States)

Publication Date:: 2018-02-20

Research Org.:: National Energy Technology Lab. (NETL), Albany, OR (United States)

Sponsoring Org.:: USDOE Office of Fossil Energy (FE)

OSTI Identifier:: 1478391

Grant/Contract Number:: SC0014506; FE0004000

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 122; Journal Issue: 13; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats


                    Gao, M. C., and Widom, M. Information Entropy of Liquid Metals.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcb.7b10723.

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                    Gao, M. C., & Widom, M. Information Entropy of Liquid Metals.  United States.  https://doi.org/10.1021/acs.jpcb.7b10723

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                    Gao, M. C., and Widom, M. Tue .  
"Information Entropy of Liquid Metals".  United States.  https://doi.org/10.1021/acs.jpcb.7b10723.  https://www.osti.gov/servlets/purl/1478391.

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@article{osti_1478391,

  title        = {Information Entropy of Liquid Metals},

  author       = {Gao, M. C. and Widom, M.},

  abstractNote = {Correlations reduce the configurational entropies of liquids below their ideal gas limits. By means of first-principles molecular dynamics simulations, we obtain accurate pair correlation functions of liquid metals, then subtract the mutual information content of these correlations from the ideal gas entropies to predict the absolute entropies over a broad range of temperatures. We apply this method to liquid aluminum and copper and demonstrate good agreement with experimental measurements; then, we apply it to predict the entropy of a liquid aluminum–copper alloy. In conclusion, corrections due to electronic entropy and many-body correlations are discussed.},

  doi          = {10.1021/acs.jpcb.7b10723},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 13,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

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Journal Article:

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https://doi.org/10.1021/acs.jpcb.7b10723

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Cited by: 5 works

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Figures / Tables:

Figure 1: (a) Radial distribution function g(r) of liquid Al at T=1000 K. (b) Contributions to the entropy of liquid Al integrated from r = 0 up to R.

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Works referenced in this record:

Microcanonical Ensemble in Quantum Statistical Mechanics
journal, October 1965

Griffiths, Robert B.
Journal of Mathematical Physics, Vol. 6, Issue 10
DOI: 10.1063/1.1704681

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
Physical Review Letters, Vol. 100, Issue 13
DOI: 10.1103/PhysRevLett.100.136406

Thermodynamic potentials and distribution functions: II. The HNC equation as an optimized superposition approximation
journal, February 1990

Hernando, J. A.
Molecular Physics, Vol. 69, Issue 2
DOI: 10.1080/00268979000100221

Excess Entropy, Diffusion Coefficient, Viscosity Coefficient and Surface Tension of Liquid Simple Metals from Diffraction Data
journal, January 2002

Yokoyama, Isao; Tsuchiya, Shusaku
MATERIALS TRANSACTIONS, Vol. 43, Issue 1
DOI: 10.2320/matertrans.43.67

Assessing the performance of recent density functionals for bulk solids
journal, April 2009

Csonka, Gábor I.; Perdew, John P.; Ruzsinszky, Adrienn
Physical Review B, Vol. 79, Issue 15
DOI: 10.1103/PhysRevB.79.155107

The free energy of the crystal-melt interface from the radial distribution function—further calculations
journal, April 1972

Ewing, R. H.
Philosophical Magazine, Vol. 25, Issue 4
DOI: 10.1080/14786437208229303

Works referencing / citing this record:

Mutual information does not detect growing correlations in the propensity of a model molecular liquid
journal, January 2019

Tripodo, Antonio; Giuntoli, Andrea; Malvaldi, Marco
Soft Matter, Vol. 15, Issue 34
DOI: 10.1039/c9sm01143a

Modeling the structure and thermodynamics of high-entropy alloys
journal, July 2018

Widom, Michael
Journal of Materials Research, Vol. 33, Issue 19
DOI: 10.1557/jmr.2018.222

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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Similar Records

Title: Information Entropy of Liquid Metals

Abstract

Citation Formats

Figures / Tables:

Microcanonical Ensemble in Quantum Statistical Mechanics journal, October 1965

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

Thermodynamic potentials and distribution functions: II. The HNC equation as an optimized superposition approximation journal, February 1990

Excess Entropy, Diffusion Coefficient, Viscosity Coefficient and Surface Tension of Liquid Simple Metals from Diffraction Data journal, January 2002

Assessing the performance of recent density functionals for bulk solids journal, April 2009

The free energy of the crystal-melt interface from the radial distribution function—further calculations journal, April 1972

Mutual information does not detect growing correlations in the propensity of a model molecular liquid journal, January 2019

Modeling the structure and thermodynamics of high-entropy alloys journal, July 2018

Microcanonical Ensemble in Quantum Statistical Mechanics
journal, October 1965

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Thermodynamic potentials and distribution functions: II. The HNC equation as an optimized superposition approximation
journal, February 1990

Excess Entropy, Diffusion Coefficient, Viscosity Coefficient and Surface Tension of Liquid Simple Metals from Diffraction Data
journal, January 2002

Assessing the performance of recent density functionals for bulk solids
journal, April 2009

The free energy of the crystal-melt interface from the radial distribution function—further calculations
journal, April 1972

Mutual information does not detect growing correlations in the propensity of a model molecular liquid
journal, January 2019

Modeling the structure and thermodynamics of high-entropy alloys
journal, July 2018