U.S. Department of Energy Office of Scientific and Technical Information
Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids
Here, we employ the Ornstein-Zernike integral equation theory with the Percus-Yevick (PY) and modified-Verlet (MV) closures to study the equilibrium structural and thermodynamic properties of metastable monodisperse hard sphere and continuous repulsion Weeks-Chandler-Andersen (WCA) fluids under density and temperature conditions where the system is strongly overcompressed or supercooled, respectively. The theoretical results are compared to crystal-avoiding simulations of these dense monodisperse model one-component fluids. The equation of state (EOS) and dimensionless compressibility are computed using both the virial and compressibility routes. For hard spheres, the MV-based virial route EOS and dimensionless compressibility are in very good agreement with simulation for all packing fractions, much better than the PY analogs. The corresponding MV-based predictions for the static structure factor are also very good. The amplitude of density fluctuations on the local cage scale and in the long wavelength limit, and three technically different measures of the density correlation length, are studied with both closures. All five properties grow in a roughly exponential manner with density in the metastable regime up to packing fractions of 58% with no sign of saturation. The MV-based results are in good agreement with our crystal-avoiding simulations. Interestingly, the density dependences of long and short wavelength quantities are closely related. The MV-based theory is also quite accurate for the thermodynamics and structure of supercooled monodisperse WCA fluids. Overall our findings are also relevant as critical input to microscopic theories that relate the equilibrium pair correlation function or static structure factor to dynamical constraints, barriers, and activated relaxation in glass-forming liquids.
Zhou, Yuxing, et al. "Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids." Physical Review. E, vol. 101, no. 4, Apr. 2020. https://doi.org/10.1103/physreve.101.042121
Zhou, Yuxing, Mei, Baicheng, & Schweizer, Kenneth S. (2020). Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids. Physical Review. E, 101(4). https://doi.org/10.1103/physreve.101.042121
Zhou, Yuxing, Mei, Baicheng, and Schweizer, Kenneth S., "Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids," Physical Review. E 101, no. 4 (2020), https://doi.org/10.1103/physreve.101.042121
@article{osti_1800525,
author = {Zhou, Yuxing and Mei, Baicheng and Schweizer, Kenneth S.},
title = {Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids},
annote = {Here, we employ the Ornstein-Zernike integral equation theory with the Percus-Yevick (PY) and modified-Verlet (MV) closures to study the equilibrium structural and thermodynamic properties of metastable monodisperse hard sphere and continuous repulsion Weeks-Chandler-Andersen (WCA) fluids under density and temperature conditions where the system is strongly overcompressed or supercooled, respectively. The theoretical results are compared to crystal-avoiding simulations of these dense monodisperse model one-component fluids. The equation of state (EOS) and dimensionless compressibility are computed using both the virial and compressibility routes. For hard spheres, the MV-based virial route EOS and dimensionless compressibility are in very good agreement with simulation for all packing fractions, much better than the PY analogs. The corresponding MV-based predictions for the static structure factor are also very good. The amplitude of density fluctuations on the local cage scale and in the long wavelength limit, and three technically different measures of the density correlation length, are studied with both closures. All five properties grow in a roughly exponential manner with density in the metastable regime up to packing fractions of 58% with no sign of saturation. The MV-based results are in good agreement with our crystal-avoiding simulations. Interestingly, the density dependences of long and short wavelength quantities are closely related. The MV-based theory is also quite accurate for the thermodynamics and structure of supercooled monodisperse WCA fluids. Overall our findings are also relevant as critical input to microscopic theories that relate the equilibrium pair correlation function or static structure factor to dynamical constraints, barriers, and activated relaxation in glass-forming liquids.},
doi = {10.1103/physreve.101.042121},
url = {https://www.osti.gov/biblio/1800525},
journal = {Physical Review. E},
issn = {ISSN 2470-0045},
number = {4},
volume = {101},
place = {United States},
publisher = {American Physical Society (APS)},
year = {2020},
month = {04}}
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 367, Issue 1909https://doi.org/10.1098/rsta.2009.0181