Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 129, Issue 24, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3046565
Keywords
chemical potential; colloids; freezing; ground states; Monte Carlo methods; suspensions
Funding
- Deutsche Forschungsgemeinschaft [B6]
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Using Monte Carlo simulations in the grand canonical and isobaric ensembles we investigate freezing phenomena in a charged colloidal suspension confined to narrow slit pores. Our model involves only the macroions which interact via a Derjaguin-Landau-Verwey-Overbeek (DLVO) potential supplemented by a soft-sphere potential. We focus on DLVO parameters typical for moderately charged silica particles (with charges Z similar to 35) in solvents of low ionic strengths. The corresponding DLVO interactions are too weak to drive a (bulk) freezing transition. Nevertheless, for sufficiently small surface separations L-z the confined systems display not only layering but also significant in-plane crystalline order at chemical potentials where the bulk system is a globally stable fluid (capillary freezing). At confinement conditions related to two-layer systems the observed in-plane structures are consistent with those detected in ground state calculations for perfect Yukawa bilayers [R. Messina and H. Lowen, Phys. Rev. Lett. 91, 146101 (2003)]. Here we additionally observe (at fixed L-z) a compression-induced first-order phase transition from a two-layer to a three-layer system with different in-plane structure, in agreement with previous findings for pure hard spheres.
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