Nonlinear Dynamics and Nucleation Kinetics in Near-Critical Liquids

The objective of our study is to model the nonlinear behavior of a near-critical liquid following a rapid change of the temperature and/or other thermodynamic parameters (pressure, external electric or gravitational field). The thermodynamic critical point is manifested by large, strongly correlated fluctuations of the order parameter (particle density in liquid-gas systems, concentration in binary solutions) in the critical range of scales. The largest critical length scale is the correlation radius r(sub c). According to the scaling theory, r(sub c) increases as r(sub c) = r(sub 0)epsilon(exp -alpha) when the nondimensional distance epsilon = (T - T(sub c))/T(sub c) to the critical point decreases. The normal gravity alters the nature of correlated long-range fluctuations when one reaches epsilon approximately equal to 10(exp -5), and correspondingly the relaxation time, tau(r(sub c)), is approximately equal to 10(exp -3) seconds; this time is short when compared to the typical experimental time. Close to the critical point, a rapid, relatively small temperature change may perturb the thermodynamic equilibrium on many scales. The critical fluctuations have a hierarchical structure, and the relaxation involves many length and time scales. Above the critical point, in the one-phase region, we consider the relaxation of the liquid following a sudden temperature change that simultaneously violates the equilibrium on many scales. Below T(sub c), a non-equilibrium state may include a distribution of small scale phase droplets; we consider the relaxation of such a droplet following a temperature change that has made the phase of the matrix stable

Microphase separation as the cause of structural complexity in 2D liquids

Under certain thermodynamic conditions, a two-dimensional liquid becomes a statistically stable mosaic of small differently-ordered clusters. We apply to this mosaic a special coarsening procedure that accounts for short-time average and topologic features of a particle near environments. We then show that the coarsened mosaic consists of two different components separated at the length-scale of few inter-particle distances. Using bond order parameters and bond lengths as instant local characteristics, we show that these components have internal properties of spatially heterogeneous crystalline or amorphous phases, so the coarsened mosaic can be seen as a microphase-separated state. We discuss general conditions favouring stability of the mosaic state, and suggest some systems for searching for this special state of matter

Ultrasensitive detection of toxic cations through changes in the tunnelling current across films of striped nanoparticles

Although multiple methods have been developed to detect metal cations, only a few offer sensitivities below 1 pM, and many require complicated procedures and sophisticated equipment. Here, we describe a class of simple solid-state sensors for the ultrasensitive detection of heavy-metal cations (notably, an unprecedented attomolar limit for the detection of CH3Hg+ in both standardized solutions and environmental samples) through changes in the tunnelling current across films of nanoparticles (NPs) protected with striped monolayers of organic ligands. The sensors are also highly selective because of the ligand-shell organization of the NPs. On binding of metal cations, the electronic structure of the molecular bridges between proximal NPs changes, the tunnelling current increases and highly conductive paths ultimately percolate the entire film. The nanoscale heterogeneity of the structure of the film broadens the range of the cation-binding constants, which leads to wide sensitivity ranges (remarkably, over 18 orders of magnitude in CH3Hg+ concentration)

Melting in 2D Lennard-Jones Systems: What Type of Phase Transition?

A typical configuration of an equilibrium 2D system of 2500 Lennard-Jones particles at melting is found to be a mosaic of crystallites and amorphous clusters. This mosaic significantly changed at times around the period tau of local vibrations, while most particles retain their nearest neighbors for times much longer than tau. In a system of 2500 particles, we found no phase separation for length scales larger than that of a crystallite. With decreasing density, the number of small amorphous clusters increased, and proliferation and percolation of amorphous matter separated the crystalline-ordered parts so that correlations between local order orientations of remote crystallites disappeared. We suggest that the mosaic is a manifestation of diminished stability of the crystalline structure resulting from competition between attraction and repulsion forces