Formation of crystal nucleus from liquid.pdf

Formation of a crystal nucleus from liquid Takeshi Kawasaki and Hajime Tanaka1 Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan Edited by Noel A. Clark, University of Colorado, Boulder, CO, and approved June 30, 2010 (received for review January 27, 2010) Crystallization is one of the most fundamental nonequilibrium phenomena universal to a variety of materials. It has so far been assumed that a supercooled liquid is in a “homogeneous disor- dered state” before crystallization. Contrary to this common belief, we reveal that a supercooled colloidal liquid is actually not homo- geneous, but has transient medium-range structural order. We find that nucleation preferentially takes place in regions of high struc- tural order via wetting effects, which reduce the crystal–liquid in- terfacial energy significantly and thus promotes crystal nucleation. This novel scenario provides a clue to solving a long-standing mys- tery concerning a large discrepancy between the rigorous numer- ical estimation of the nucleation rate on the basis of the classical nucleation theory and the experimentally observed ones. Our find- ingmay shed light not only on themechanism of crystal nucleation, but also on the fundamental nature of a supercooled liquid state. bond orientational order ∣ glass transition ∣ hard-sphere liquid ∣ metastable liquid Crystallization is a process in which an ordered phase emergesfrom a disordered state. It is important not only as a funda- mental problem of nonequilibrium statistical physics, but also as that of materials science. The initial state is a disordered liquid and the final state is a stable crystal. The classical nucleation the- ory (1–3) considers these initial homogeneous disordered liquid and final ordered crystal phases as the only key players of nuclea- tion. In this theory, thus, crystal nucleation is controlled by the competition between the free-energy gain due to the liquid–crys- tal transforma