INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS: CONDENSED MATTER J. Phys.: Condens. Matter 18 (2006) R15–R68 doi:10.1088/0953-8984/18/6/R01 TOPICAL REVIEW Effects of confinement on freezing and melting C Alba-Simionesco 1 , B Coasne 2 , G Dosseh 1 , G Dudziak 3 , K E Gubbins 2 , R Radhakrishnan 4 and M Sliwinska-Bartkowiak 3 1 Laboratoire de Chimie Physique, CNRS-UMR 8000, Bˆ atiment 349, Universit´ e de Paris-Sud, F-91405 Orsay, France 2 Center for High Performance Simulation and Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, NC 27695-7905, USA 3 Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan, Poland 4 Department of Bioengineering, University of Pennsylvania, Philadelphia, PA 19104, USA Received 15 August 2005, in final form 21 November 2005 Published 23 January 2006 Online at stacks.iop.org/JPhysCM/18/R15 Abstract We present a review of experimental, theoretical, and molecular simulation studies of confinement effects on freezing and melting. We consider both simple and more complex adsorbates that are confined in various environments (slit or cylindrical pores and also disordered porous materials). The most commonly used molecular simulation, theoretical and experimental methods are first presented. We also provide a brief description of the most widely used porous materials. The current state of knowledge on the effects of confinement on structure and freezing temperature, and the appearance of new surface- driven and confinement-driven phases are then discussed. We also address how confinement affects the glass transition. Contents 1. Introduction 16 2. Methods and materials 19 2.1. Porous materials 19 2.2. Experimental methods 23 2.3. Molecular simulation and theoretical methods 30 3. Effect of confinement on structure and freezing temperature 37 3.1. Simple systems 37 3.2. Complex systems 44 4. New surface-driven and confinement-driven phases 49 4.1. Contact layer phases 49 4.2. Hexatic phase and two-dimensional melting 50 4.3. Glass transition in nanoporous materials 52 5. Global phase diagrams 57 6. Conclusion 59 0953-8984/06/060015+54$30.00 © 2006 IOP Publishing Ltd Printed in the UK R15