Mikael C. Rechtsman
Department of Physics, Princeton University, Princeton, New Jersey 08544, USA

F. H. Stillinger
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA

S. Torquato
Department of Physics, and Department of Chemistry, Princeton University, Princeton, New Jersey 08544, Program in Applied and Computational Mathematics and PRISM, and Princeton Center for Theoretical Physics, Princeton, New Jersey, 08544

J. Phys. Chem. A 111, 12816-12821 (2007). [G. Scoles special issue]

Received August 27, 2007; In Final Form: October 10, 2007.

Abstract

We have devised an isotropic interaction potential that gives rise to negative thermal expansion (NTE) behavior in equilibrium many-particle systems in both two and three dimensions over a wide temperature and pressure range (including zero pressure). An optimization procedure is used in order to find a potential that yields a strong NTE effect. A key feature of the potential that gives rise to this behavior is the softened interior of its basin of attraction. Although such anomalous behavior is well-known in material systems with directional interactions (e.g., zirconium tungstate), to our knowledge, this is the first time that NTE behavior has been established to occur in single-component many-particle systems for isotropic interactions. Using constantpressure Monte Carlo simulations, we show that as the temperature is increased, the system exhibits negative, zero, and then positive thermal expansion before melting (for both two- and three-dimensional systems). The behavior is explicitly compared to that of a Lennard-Jones system, which exhibits typical expansion upon heating for all temperatures and pressures.