Thermodynamics of d-dimensional hard sphere fluids confined to micropores

  • Hyungjun Kim
  • , William A. Goddard
  • , Kyeong Hwan Han
  • , Changho Kim
  • , Eok Kyun Lee
  • , Peter Talkner
  • , Peter Hnggi

Research output: Contribution to journalArticlepeer-review

Abstract

We derive an analytical expression of the second virial coefficient of d-dimensional hard sphere fluids confined to slit pores by applying Speedy and Reiss' interpretation of cavity space. We confirm that this coefficient is identical to the one obtained from the Mayer cluster expansion up to second order with respect to fugacity. The key step of both approaches is to evaluate either the surface area or the volume of the d-dimensional exclusion sphere confined to a slit pore. We, further, present an analytical form of thermodynamic functions such as entropy and pressure tensor as a function of the size of the slit pore. Molecular dynamics simulations are performed for d 2 and d 3, and the results are compared with analytically obtained equations of state. They agree satisfactorily in the low density regime, and, for given density, the agreement of the results becomes excellent as the width of the slit pore gets smaller, because the higher order virial coefficients become unimportant.

Original languageEnglish
Article number114502
JournalJournal of Chemical Physics
Volume134
Issue number11
DOIs
Publication statusPublished - 21 Mar 2011
Externally publishedYes

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