Spatial confinement effect on the atomic structure of solid argon

Abstract

Molecules confined in nanopores show unusual behavior not seen in bulk systems. The present paper reports on molecular dynamics simulations of unusual freezing behavior in confined Ar. Similar to bulk Ar, liquid Ar confined in pores with a diameter D>15σ (5.1 nm), where σ is the diameter of the Ar atom, crystallizes when the cooling rate is lower than a critical value (Qc). We also find that the spatial confinement does not have significant influence on Qc when D>15σ (5.1 nm). In the pore of 10σ (3.4 nm) in diameter, on the other hand, the behavior is dramatically changed. Crystalline Ar does not appear inside the pore even when the system is cooled at a rate lower than the Qc in the bulk system by over two orders of magnitude. Instead, amorphous Ar characterized by local icosahedral configurations is formed in the pore. We further find that, even when crystalline Ar is formed outside the pore, it does not grow deeply into the pore. This supports that the amorphous Ar is actually the most stable phase in the pore. It is well known that Ar is a poor glass former. Our finding that even such an amorphous Ar is the most stable in the pore suggests that, in any system, it is possible to prepare amorphous structure selectively by using nano-molds. © 2005 American Institute of Physics.