Building upon past work on the phase diagram of Janus fluids [F. Sciortino, A. Giacometti, and G. Pastore, Phys. Rev. Lett. 103, 237801 (2009)], we perform a detailed study of integral equation theory of the Kern-Frenkel potential with coverage that is tuned from the isotropic square-well fluid to the Janus limit. An improved algorithm for the reference hypernetted-chain (RHNC) equation for this problem is implemented that significantly extends the range of applicability of RHNC. Results for both structure and thermodynamics are presented and compared with numerical simulations. Unlike previous attempts, this algorithm is shown to be stable down to the Janus limit, thus paving the way for analyzing the frustration mechanism characteristic of the gas-liquid transition in the Janus system. The results are also compared with Barker-Henderson thermodynamic perturbation theory on the same model. We then discuss the pros and cons of both approaches within a unified treatment. On balance, RHNC integral equation theory, even with an isotropic hard-sphere reference system, is found to be a good compromise between accuracy of the results, computational effort, and uniform quality to tackle self-assembly processes in patchy colloids of complex nature. Further improvement in RHNC however clearly requires an anisotropic reference bridge function.

From square-well to Janus: Improved algorithm for integral equation theory and comparison with thermodynamic perturbation theory within the Kern-Frenkel model

GIACOMETTI, Achille;
2014-01-01

Abstract

Building upon past work on the phase diagram of Janus fluids [F. Sciortino, A. Giacometti, and G. Pastore, Phys. Rev. Lett. 103, 237801 (2009)], we perform a detailed study of integral equation theory of the Kern-Frenkel potential with coverage that is tuned from the isotropic square-well fluid to the Janus limit. An improved algorithm for the reference hypernetted-chain (RHNC) equation for this problem is implemented that significantly extends the range of applicability of RHNC. Results for both structure and thermodynamics are presented and compared with numerical simulations. Unlike previous attempts, this algorithm is shown to be stable down to the Janus limit, thus paving the way for analyzing the frustration mechanism characteristic of the gas-liquid transition in the Janus system. The results are also compared with Barker-Henderson thermodynamic perturbation theory on the same model. We then discuss the pros and cons of both approaches within a unified treatment. On balance, RHNC integral equation theory, even with an isotropic hard-sphere reference system, is found to be a good compromise between accuracy of the results, computational effort, and uniform quality to tackle self-assembly processes in patchy colloids of complex nature. Further improvement in RHNC however clearly requires an anisotropic reference bridge function.
2014
140
File in questo prodotto:
File Dimensione Formato  
Giacometti_JCP_14.pdf

non disponibili

Tipologia: Documento in Post-print
Licenza: Accesso chiuso-personale
Dimensione 1.62 MB
Formato Adobe PDF
1.62 MB Adobe PDF   Visualizza/Apri

I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/39714
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 20
  • ???jsp.display-item.citation.isi??? 18
social impact