Observation of Single Transits in Supercooled Monatomic Liquids

A transit is the motion of a system from one many-particle potential energy valley to another. We report the observation of transits in molecular dynamics (MD) calculations of supercooled liquid argon and sodium. Each transit is a correlated simultaneous shift in the equilibrium positions of a small local group of particles, as revealed in the fluctuating graphs of the particle coordinates versus time. This is the first reported direct observation of transit motion in a monatomic liquid in thermal equilibrium. We found transits involving 2 to 11 particles, having mean shift in equilibrium position on the order of 0.4 R_1 in argon and 0.25 R_1 in sodium, where R_1 is the nearest neighbor distance. The time it takes for a transit to occur is approximately one mean vibrational period, confirming that transits are fast.Comment: 19 pages, 8 figure

Hydrophobic interactions: an overview

We present an overview of the recent progress that has been made in understanding the origin of hydrophobic interactions. We discuss the different character of the solvation behavior of apolar solutes at small and large length scales. We emphasize that the crossover in the solvation behavior arises from a collective effect, which means that implicit solvent models should be used with care. We then discuss a recently developed explicit solvent model, in which the solvent is not described at the atomic level, but rather at the level of a density field. The model is based upon a lattice-gas model, which describes density fluctuations in the solvent at large length scales, and a Gaussian model, which describes density fluctuations at smaller length scales. By integrating out the small length scale field, a Hamiltonian is obtained, which is a function of the binary, large-length scale field only. This makes it possible to simulate much larger systems than hitherto possible as demonstrated by the application of the model to the collapse of an ideal hydrophobic polymer. The results show that the collapse is dominated by the dynamics of the solvent, in particular the formation of a vapor bubble of critical size. Implications of these findings to the understanding of pressure denaturation of proteins are discussed.Comment: 10 pages, 4 figure

Inherent-Structure Dynamics and Diffusion in Liquids

The self-diffusion constant D is expressed in terms of transitions among the local minima of the potential (inherent structure, IS) and their correlations. The formulae are evaluated and tested against simulation in the supercooled, unit-density Lennard-Jones liquid. The approximation of uncorrelated IS-transition (IST) vectors, D_{0}, greatly exceeds D in the upper temperature range, but merges with simulation at reduced T ~ 0.50. Since uncorrelated IST are associated with a hopping mechanism, the condition D ~ D_{0} provides a new way to identify the crossover to hopping. The results suggest that theories of diffusion in deeply supercooled liquids may be based on weakly correlated IST.Comment: submitted to PR

Forced motion of a probe particle near the colloidal glass transition

We use confocal microscopy to study the motion of a magnetic bead in a dense colloidal suspension, near the colloidal glass transition volume fraction $\phi_g$. For dense liquid-like samples near $\phi_g$, below a threshold force the magnetic bead exhibits only localized caged motion. Above this force, the bead is pulled with a fluctuating velocity. The relationship between force and velocity becomes increasingly nonlinear as $\phi_g$ is approached. The threshold force and nonlinear drag force vary strongly with the volume fraction, while the velocity fluctuations do not change near the transition.Comment: 7 pages, 4 figures revised version, accepted for publication in Europhysics Letter

Exact Criterion for Determining Clustering vs. Reentrant Melting Behavior for Bounded Interaction Potentials

We examine in full generality the phase behavior of systems whose constituent particles interact by means of potentials which do not diverge at the origin, are free of attractive parts and decay fast enough to zero as the interparticle separation r goes to infinity. By employing a mean field-density functional theory which is shown to become exact at high temperatures and/or densities, we establish a criterion which determines whether a given system will freeze at all temperatures or it will display reentrant melting and an upper freezing temperature.Comment: 5 pages, 3 figures, submitted to PRL on March 29, 2000 New version: 10 pages, 9 figures, forwarded to PRE on October 16, 200

What does the potential energy landscape tell us about the dynamics of supercooled liquids and glasses?

For a model glass-former we demonstrate via computer simulations how macroscopic dynamic quantities can be inferred from a PEL analysis. The essential step is to consider whole superstructures of many PEL minima, called metabasins, rather than single minima. We show that two types of metabasins exist: some allowing for quasi-free motion on the PEL (liquid-like), the others acting as traps (solid-like). The activated, multi-step escapes from the latter metabasins are found to dictate the slowing down of dynamics upon cooling over a much broader temperature range than is currently assumed

The Potential Energy Landscape and Mechanisms of Diffusion in Liquids

The mechanism of diffusion in supercooled liquids is investigated from the potential energy landscape point of view, with emphasis on the crossover from high- to low-T dynamics. Molecular dynamics simulations with a time dependent mapping to the associated local mininum or inherent structure (IS) are performed on unit-density Lennard-Jones (LJ). New dynamical quantities introduced include r2_{is}(t), the mean-square displacement (MSD) within a basin of attraction of an IS, R2(t), the MSD of the IS itself, and g_{loc}(t) the mean waiting time in a cooperative region. At intermediate T, r2_{is}(t) posesses an interval of linear t-dependence allowing calculation of an intrabasin diffusion constant D_{is}. Near T_{c} diffusion is intrabasin dominated with D = D_{is}. Below T_{c} the local waiting time tau_{loc} exceeds the time, tau_{pl}, needed for the system to explore the basin, indicating the action of barriers. The distinction between motion among the IS below T_{c} and saddle, or border dynamics above T_{c} is discussed.Comment: submitted to pr

The potential energy landscape of a model glass former: thermodynamics, anharmonicities, and finite size effects

It is possible to formulate the thermodynamics of a glass forming system in terms of the properties of inherent structures, which correspond to the minima of the potential energy and build up the potential energy landscape in the high-dimensional configuration space. In this work we quantitatively apply this general approach to a simulated model glass-forming system. We systematically vary the system size between N=20 and N=160. This analysis enables us to determine for which temperature range the properties of the glass former are governed by the regions of the configuration space, close to the inherent structures. Furthermore, we obtain detailed information about the nature of anharmonic contributions. Moreover, we can explain the presence of finite size effects in terms of specific properties of the energy landscape. Finally, determination of the total number of inherent structures for very small systems enables us to estimate the Kauzmann temperature

Computer investigation of the energy landscape of amorphous silica

The multidimensional topography of the collective potential energy function of a so-called strong glass former (silica) is analyzed by means of classical molecular dynamics calculations. Features qualitatively similar to those of fragile glasses are recovered at high temperatures : in particular an intrinsic characteristic temperature $T_c\simeq 3500$K is evidenced above which the system starts to investigate non-harmonic potential energy basins. It is shown that the anharmonicities are essentially characterized by a roughness appearing in the potential energy valleys explored by the system for temperatures above $T_c$.Comment: 5 pages; accepted for publication in PR

Spectral Signatures of the Diffusional Anomaly in Water

Analysis of power spectrum profiles for various tagged particle quantities in bulk SPC/E water is used to demonstrate that variations in mobility associated with the diffusional anomaly are mirrored in the exponent of the \onebyf\ region. Monitoring of \onebyf behaviour is shown to be a simple and direct method for linking phenomena on three distinctive length and time scales: the local molecular environment, hydrogen bond network reorganisations and the diffusivity. The results indicate that experimental studies of supercooled water to probe the density dependence of $1/f^\alpha$ spectral features, or equivalent stretched exponential behaviour in time-correlation functions, will be of interest.Comment: 5 Pages, 4 Figure