Two-body perturbation theory versus first order perturbation theory: A comparison based on the square-well fluid

Luís Fernando Mercier Franco, Marcelo Castier, Ioannis Economou

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

We show that the Zwanzig first-order perturbation theory can be obtained directly from a truncated Taylor series expansion of a two-body perturbation theory and that such truncation provides a more accurate prediction of thermodynamic properties than the full two-body perturbation theory. This unexpected result is explained by the quality of the resulting approximation for the fluid radial distribution function. We prove that the first-order and the two-body perturbation theories are based on different approximations for the fluid radial distribution function. To illustrate the calculations, the square-well fluid is adopted. We develop an analytical expression for the two-body perturbed Helmholtz free energy for the square-well fluid. The equation of state obtained using such an expression is compared to the equation of state obtained from the first-order approximation. The vapor-liquid coexistence curve and the supercritical compressibility factor of a square-well fluid are calculated using both equations of state and compared to Monte Carlo simulation data. Finally, we show that the approximation for the fluid radial distribution function given by the first-order perturbation theory provides closer values to the ones calculated via Monte Carlo simulations. This explains why such theory gives a better description of the fluid thermodynamic behavior.

Original languageEnglish
Article number214108
JournalJournal of Chemical Physics
Volume147
Issue number21
DOIs
Publication statusPublished - 7 Dec 2017

Fingerprint

square wells
perturbation theory
Fluids
fluids
Equations of state
radial distribution
Distribution functions
approximation
equations of state
distribution functions
Taylor series
data simulation
series expansion
Compressibility
Free energy
compressibility
Thermodynamic properties
thermodynamic properties
free energy
Vapors

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Two-body perturbation theory versus first order perturbation theory : A comparison based on the square-well fluid. / Mercier Franco, Luís Fernando; Castier, Marcelo; Economou, Ioannis.

In: Journal of Chemical Physics, Vol. 147, No. 21, 214108, 07.12.2017.

Research output: Contribution to journalArticle

@article{dd541da7e0414fa0b00e37802638e7cf,
title = "Two-body perturbation theory versus first order perturbation theory: A comparison based on the square-well fluid",
abstract = "We show that the Zwanzig first-order perturbation theory can be obtained directly from a truncated Taylor series expansion of a two-body perturbation theory and that such truncation provides a more accurate prediction of thermodynamic properties than the full two-body perturbation theory. This unexpected result is explained by the quality of the resulting approximation for the fluid radial distribution function. We prove that the first-order and the two-body perturbation theories are based on different approximations for the fluid radial distribution function. To illustrate the calculations, the square-well fluid is adopted. We develop an analytical expression for the two-body perturbed Helmholtz free energy for the square-well fluid. The equation of state obtained using such an expression is compared to the equation of state obtained from the first-order approximation. The vapor-liquid coexistence curve and the supercritical compressibility factor of a square-well fluid are calculated using both equations of state and compared to Monte Carlo simulation data. Finally, we show that the approximation for the fluid radial distribution function given by the first-order perturbation theory provides closer values to the ones calculated via Monte Carlo simulations. This explains why such theory gives a better description of the fluid thermodynamic behavior.",
author = "{Mercier Franco}, {Lu{\'i}s Fernando} and Marcelo Castier and Ioannis Economou",
year = "2017",
month = "12",
day = "7",
doi = "10.1063/1.4994823",
language = "English",
volume = "147",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "21",

}

TY - JOUR

T1 - Two-body perturbation theory versus first order perturbation theory

T2 - A comparison based on the square-well fluid

AU - Mercier Franco, Luís Fernando

AU - Castier, Marcelo

AU - Economou, Ioannis

PY - 2017/12/7

Y1 - 2017/12/7

N2 - We show that the Zwanzig first-order perturbation theory can be obtained directly from a truncated Taylor series expansion of a two-body perturbation theory and that such truncation provides a more accurate prediction of thermodynamic properties than the full two-body perturbation theory. This unexpected result is explained by the quality of the resulting approximation for the fluid radial distribution function. We prove that the first-order and the two-body perturbation theories are based on different approximations for the fluid radial distribution function. To illustrate the calculations, the square-well fluid is adopted. We develop an analytical expression for the two-body perturbed Helmholtz free energy for the square-well fluid. The equation of state obtained using such an expression is compared to the equation of state obtained from the first-order approximation. The vapor-liquid coexistence curve and the supercritical compressibility factor of a square-well fluid are calculated using both equations of state and compared to Monte Carlo simulation data. Finally, we show that the approximation for the fluid radial distribution function given by the first-order perturbation theory provides closer values to the ones calculated via Monte Carlo simulations. This explains why such theory gives a better description of the fluid thermodynamic behavior.

AB - We show that the Zwanzig first-order perturbation theory can be obtained directly from a truncated Taylor series expansion of a two-body perturbation theory and that such truncation provides a more accurate prediction of thermodynamic properties than the full two-body perturbation theory. This unexpected result is explained by the quality of the resulting approximation for the fluid radial distribution function. We prove that the first-order and the two-body perturbation theories are based on different approximations for the fluid radial distribution function. To illustrate the calculations, the square-well fluid is adopted. We develop an analytical expression for the two-body perturbed Helmholtz free energy for the square-well fluid. The equation of state obtained using such an expression is compared to the equation of state obtained from the first-order approximation. The vapor-liquid coexistence curve and the supercritical compressibility factor of a square-well fluid are calculated using both equations of state and compared to Monte Carlo simulation data. Finally, we show that the approximation for the fluid radial distribution function given by the first-order perturbation theory provides closer values to the ones calculated via Monte Carlo simulations. This explains why such theory gives a better description of the fluid thermodynamic behavior.

UR - http://www.scopus.com/inward/record.url?scp=85037689877&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85037689877&partnerID=8YFLogxK

U2 - 10.1063/1.4994823

DO - 10.1063/1.4994823

M3 - Article

AN - SCOPUS:85037689877

VL - 147

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 21

M1 - 214108

ER -