Equilibrium phase behavior of polydisperse hard spheres

被引:116
作者
Fasolo, M [1 ]
Sollich, P [1 ]
机构
[1] Kings Coll London, Dept Math, London WC2R 2LS, England
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1103/PhysRevLett.91.068301
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
We calculate the phase behavior of hard spheres with size polydispersity, using accurate free energies for the fluid and solid phases. Cloud and shadow curves are found exactly by the moment free energy method, but we also compute the complete phase diagram, taking full account of fractionation. In contrast to earlier, simplified treatments we find no point of equal concentration between fluid and solid or reentrant melting at higher densities. Rather, the fluid cloud curve continues to the largest polydispersity that we study (14%); from the equilibrium phase behavior a terminal polydispersity can thus be defined only for the solid, where we find it to be around 7%. At sufficiently large polydispersity, fractionation into several solid phases can occur, consistent with previous approximate calculations; we find, in addition, that coexistence of several solids with a fluid phase is also possible.
引用
收藏
页码:1 / 068301
页数:4
相关论文
共 34 条
[1]   Suppression of crystal nucleation in polydisperse colloids due to increase of the surface free energy [J].
Auer, S ;
Frenkel, D .
NATURE, 2001, 413 (6857) :711-713
[2]   ON THE STABILITY OF POLYDISPERSE COLLOIDAL CRYSTALS [J].
BARRAT, JL ;
HANSEN, JP .
JOURNAL DE PHYSIQUE, 1986, 47 (09) :1547-1553
[3]   A geometrically-based mean-field theory of polydisperse hard-sphere mixtures [J].
Bartlett, P .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (01) :188-196
[4]   Reentrant melting in polydispersed hard spheres [J].
Bartlett, P ;
Warren, PB .
PHYSICAL REVIEW LETTERS, 1999, 82 (09) :1979-1982
[5]   Thermodynamic properties of polydisperse hard spheres [J].
Bartlett, P .
MOLECULAR PHYSICS, 1999, 97 (05) :685-693
[6]   Fractionated crystallization in a polydisperse mixture of hard spheres [J].
Bartlett, P .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (24) :10970-10975
[7]   Monte carlo study of freezing of polydisperse hard spheres [J].
Bolhuis, PG ;
Kofke, DA .
PHYSICAL REVIEW E, 1996, 54 (01) :634-643
[8]   Numerical study of freezing in polydisperse colloidal suspensions [J].
Bolhuis, PG ;
Kofke, DA .
JOURNAL OF PHYSICS-CONDENSED MATTER, 1996, 8 (47) :9627-9631
[9]   HARD-SPHERE EQUATION OF STATE [J].
BOUBLIK, T .
JOURNAL OF CHEMICAL PHYSICS, 1970, 53 (01) :471-&
[10]   Phase equilibria in the polydisperse Zwanzig model of hard rods [J].
Clarke, N ;
Cuesta, JA ;
Sear, R ;
Sollich, P ;
Speranza, A .
JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (14) :5817-5829