Application of integral equation theories to predict the structure, thermodynamics, and phase-behavior of water

L. Lue, D. Blankschtein

Research output: Contribution to journalArticle

56 Citations (Scopus)

Abstract

We analyze the predictive capabilities of the site?site Ornstein?Zernike equation and the Chandler? Silbey?Ladanyi equations for various potential models of water. Specifically, we solve ~i! the site?site Ornstein?Zernike equation with the hypernetted-chain closure, and ~ii! the Chandler? Silbey?Ladanyi equations with the hypernetted-chain closure as well as with the zeroth-order bridge functions, and compare their predictions of the structure, thermodynamics, and phase behavior of water with those obtained from computer simulations and experimental measurements. The predictions of the various site?site pair correlation functions of water for both integral equations are comparable. However, the Chandler?Silbey?Ladanyi equations seem to better predict the structure of the fluid beyond the first coordination shell. In addition, the Chandler?Silbey?Ladanyi equations provide better estimates of the thermodynamic properties of water as compared to those of the site?site Ornstein?Zernike equation, when the results are compared with those of computer simulations. We also predict the liquid?vapor coexistence curve and the vapor pressure of water using both integral equations. The Chandler?Silbey?Ladanyi equations predict higher densities of the coexisting liquid and vapor branches as compared to those predicted by the site?site Ornstein? Zernike equation. The predictions of the Chandler?Silbey?Ladanyi equations for the liquid branch are found to be in better agreement with the computer simulations data, while the site?site Ornstein?Zernike equation is found to work better for the vapor branch. The vapor pressure predictions of the site?site Ornstein?Zernike equation are found to be in good agreement with the experimental values, while the Chandler?Silbey?Ladanyi equations are found to give slightly higher predictions of the vapor pressure.
LanguageEnglish
Pages5427-5437
Number of pages11
JournalJournal of Chemical Physics
Volume102
Issue number13
DOIs
Publication statusPublished - 1 Apr 1995

Fingerprint

Phase behavior
Integral equations
integral equations
Thermodynamics
thermodynamics
Vapor pressure
Water
water
Vapors
Computer simulation
Liquids
vapor pressure
predictions
computerized simulation
vapors
Thermodynamic properties
closures
liquids
Fluids
thermodynamic properties

Keywords

  • liquid water
  • molecular fluids
  • free-energy
  • potentials
  • compressibility
  • approximation
  • simulation
  • solvation

Cite this

@article{9e14d542ee6b4fb59eb4d7a3f09886bc,
title = "Application of integral equation theories to predict the structure, thermodynamics, and phase-behavior of water",
abstract = "We analyze the predictive capabilities of the site?site Ornstein?Zernike equation and the Chandler? Silbey?Ladanyi equations for various potential models of water. Specifically, we solve ~i! the site?site Ornstein?Zernike equation with the hypernetted-chain closure, and ~ii! the Chandler? Silbey?Ladanyi equations with the hypernetted-chain closure as well as with the zeroth-order bridge functions, and compare their predictions of the structure, thermodynamics, and phase behavior of water with those obtained from computer simulations and experimental measurements. The predictions of the various site?site pair correlation functions of water for both integral equations are comparable. However, the Chandler?Silbey?Ladanyi equations seem to better predict the structure of the fluid beyond the first coordination shell. In addition, the Chandler?Silbey?Ladanyi equations provide better estimates of the thermodynamic properties of water as compared to those of the site?site Ornstein?Zernike equation, when the results are compared with those of computer simulations. We also predict the liquid?vapor coexistence curve and the vapor pressure of water using both integral equations. The Chandler?Silbey?Ladanyi equations predict higher densities of the coexisting liquid and vapor branches as compared to those predicted by the site?site Ornstein? Zernike equation. The predictions of the Chandler?Silbey?Ladanyi equations for the liquid branch are found to be in better agreement with the computer simulations data, while the site?site Ornstein?Zernike equation is found to work better for the vapor branch. The vapor pressure predictions of the site?site Ornstein?Zernike equation are found to be in good agreement with the experimental values, while the Chandler?Silbey?Ladanyi equations are found to give slightly higher predictions of the vapor pressure.",
keywords = "liquid water, molecular fluids, free-energy, potentials, compressibility, approximation, simulation, solvation",
author = "L. Lue and D. Blankschtein",
note = "English Article QP515 J CHEM PHYS",
year = "1995",
month = "4",
day = "1",
doi = "10.1063/1.469270",
language = "English",
volume = "102",
pages = "5427--5437",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
number = "13",

}

Application of integral equation theories to predict the structure, thermodynamics, and phase-behavior of water. / Lue, L.; Blankschtein, D.

In: Journal of Chemical Physics, Vol. 102, No. 13, 01.04.1995, p. 5427-5437.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Application of integral equation theories to predict the structure, thermodynamics, and phase-behavior of water

AU - Lue, L.

AU - Blankschtein, D.

N1 - English Article QP515 J CHEM PHYS

PY - 1995/4/1

Y1 - 1995/4/1

N2 - We analyze the predictive capabilities of the site?site Ornstein?Zernike equation and the Chandler? Silbey?Ladanyi equations for various potential models of water. Specifically, we solve ~i! the site?site Ornstein?Zernike equation with the hypernetted-chain closure, and ~ii! the Chandler? Silbey?Ladanyi equations with the hypernetted-chain closure as well as with the zeroth-order bridge functions, and compare their predictions of the structure, thermodynamics, and phase behavior of water with those obtained from computer simulations and experimental measurements. The predictions of the various site?site pair correlation functions of water for both integral equations are comparable. However, the Chandler?Silbey?Ladanyi equations seem to better predict the structure of the fluid beyond the first coordination shell. In addition, the Chandler?Silbey?Ladanyi equations provide better estimates of the thermodynamic properties of water as compared to those of the site?site Ornstein?Zernike equation, when the results are compared with those of computer simulations. We also predict the liquid?vapor coexistence curve and the vapor pressure of water using both integral equations. The Chandler?Silbey?Ladanyi equations predict higher densities of the coexisting liquid and vapor branches as compared to those predicted by the site?site Ornstein? Zernike equation. The predictions of the Chandler?Silbey?Ladanyi equations for the liquid branch are found to be in better agreement with the computer simulations data, while the site?site Ornstein?Zernike equation is found to work better for the vapor branch. The vapor pressure predictions of the site?site Ornstein?Zernike equation are found to be in good agreement with the experimental values, while the Chandler?Silbey?Ladanyi equations are found to give slightly higher predictions of the vapor pressure.

AB - We analyze the predictive capabilities of the site?site Ornstein?Zernike equation and the Chandler? Silbey?Ladanyi equations for various potential models of water. Specifically, we solve ~i! the site?site Ornstein?Zernike equation with the hypernetted-chain closure, and ~ii! the Chandler? Silbey?Ladanyi equations with the hypernetted-chain closure as well as with the zeroth-order bridge functions, and compare their predictions of the structure, thermodynamics, and phase behavior of water with those obtained from computer simulations and experimental measurements. The predictions of the various site?site pair correlation functions of water for both integral equations are comparable. However, the Chandler?Silbey?Ladanyi equations seem to better predict the structure of the fluid beyond the first coordination shell. In addition, the Chandler?Silbey?Ladanyi equations provide better estimates of the thermodynamic properties of water as compared to those of the site?site Ornstein?Zernike equation, when the results are compared with those of computer simulations. We also predict the liquid?vapor coexistence curve and the vapor pressure of water using both integral equations. The Chandler?Silbey?Ladanyi equations predict higher densities of the coexisting liquid and vapor branches as compared to those predicted by the site?site Ornstein? Zernike equation. The predictions of the Chandler?Silbey?Ladanyi equations for the liquid branch are found to be in better agreement with the computer simulations data, while the site?site Ornstein?Zernike equation is found to work better for the vapor branch. The vapor pressure predictions of the site?site Ornstein?Zernike equation are found to be in good agreement with the experimental values, while the Chandler?Silbey?Ladanyi equations are found to give slightly higher predictions of the vapor pressure.

KW - liquid water

KW - molecular fluids

KW - free-energy

KW - potentials

KW - compressibility

KW - approximation

KW - simulation

KW - solvation

UR - http://jcp.aip.org/resource/1/jcpsa6/v102/i13/p5427_s1?isAuthorized=no

U2 - 10.1063/1.469270

DO - 10.1063/1.469270

M3 - Article

VL - 102

SP - 5427

EP - 5437

JO - Journal of Chemical Physics

T2 - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 13

ER -