Search results for "kinetics"

Electrocatalytic thermodynamics and kinetics at constant electrode potentials: The grand canonical ensemble approach

2020

Theory of non-equilibrium critical phenomena in three-dimensional condensed systems of charged mobile nanoparticles.

2014

A study of 3d electrostatic self-assembly (SA) in systems of charged nanoparticles (NPs) is one of the most difficult theoretical problems. In particular, the limiting case of negligible or very low polar media (e.g. salt) concentration, where the long-range NP interactions cannot be reduced to commonly used effective short-range (Yukawa) potentials, remains unstudied. Moreover, the present study has demonstrated that unlike the Debye–Huckel theory, a complete screening of the charges in SA kinetics (dynamic SA) is not always possible. Generally speaking, one has to take into account implicitly how each NP interacts with all other NPs (the true long-range interactions). Traditional theoreti…

Effect of nonequilibrium charge screening in A + B ? 0 bimolecular reactions in condensed matter

1993

The formalism of many-particle densities developed earlier by the present authors is applied to the study of the cooperative effects in the kinetics of bimolecular A +B--*0 reactions between oppositely charged particles (reactants). It is shown that unlike the Debye-Hiickel theory in statistical physics, here charge screening has essentially a nonequilibrium character. For the asymmetric mobility of reactants (DA=0, D~4:0) the joint spatial distribution of similar immobile reactants A reveals at short distances a singular character associated with their aggregation. The relevant reaction rate does not approach a steady state (as it does in the symmetric case, DA=DB), but increases infinitel…

Microscopic approach to the kinetics of pattern formation of charged molecules on surfaces.

2010

A microscopic formalism based on computing many-particle densities is applied to the analysis of the diffusion-controlled kinetics of pattern formation in oppositely charged molecules on surfaces or adsorbed at interfaces with competing long-range Coulomb and short-range Lennard-Jones interactions. Particular attention is paid to the proper molecular treatment of energetic interactions driving pattern formation in inhomogeneous systems. The reverse Monte Carlo method is used to visualize the spatial molecular distribution based on the calculated radial distribution functions (joint correlation functions). We show the formation of charge domains for certain combinations of temperature and dy…

Force-clamp spectroscopy of reversible bond breakage.

2008

We consider reversible breaking of adhesion bonds or folding of proteins under the influence of a constant external force. We discuss the stochastic properties of the unbinding/rebinding events and analyze their mean number and their variance in the framework of simple two-state models. In the calculations, we exploit the analogy to single molecule fluorescence and particularly between unbinding/rebinding and photon emission events. Environmental fluctuation models are used to describe deviations from Markovian behavior. The second moment of the event-number distribution is found to be very sensitive to possible exchange processes and can thus be used to identify temporal fluctuations of th…

Molecular-dynamics studies of annihilation reactions

2004

The validity of the reaction-diffusion formulation of annihilation kinetics, with randomly distributed initial conditions, is investigated by molecular-dynamics simulations of dense hard-disk fluids. For the reaction A + B → C + C quantitative agreement is found. Yet, this proves not to be the case for the reaction A + A → C + C, where major discrepancies are observed. For this latter reaction, more sophisticated theories predict a logarithmic decay law of the form ln (t)/t. The microscopic simulations essentially confirm this prediction.

Stability of solid T2 films

1990

Abstract Films of molecular tritium, physisorbed on a cold substrate, have been investigated by means of ellipsometry. A significant effect of the radioactive decay processes on the desorption kinetics and the low temperature stability of these films is not observed.

Size effect in phase transition kinetics

1988

The growth of a spontaneous lattice average magnetization in a magnetic system which is suddenly brought below the transition temperature is a stochastic process in which the very small fluctuations of the initial magnetization are amplified to a macroscopic size. The initial magnetization fluctuates in time around the zero average value because of the finite size of the system. As a consequence of the fluctuation-amplification phenomenon the nonlinear relaxation of the finite system is qualitatively different from that of the infinite one. The present paper studies this feature of phase-transition kinetics in the framework of a very simple model: the dynamical generalization of the spheric…

KINETICS OF CRYSTAL GROWTH LIMITED BY RANDOM VELOCITY FIELDS

2008

A spherical growth process controlled by velocity fluctuations of particles of a saturated solution is investigated. Velocity fluctuations are modeled by a Gaussian random field. The interface evolution is determined by a Langevin-type equation with a multiplicative random field, which in the case of the quasi-homogeneous random Gaussian field is equivalent to Fokker–Planck dynamics. We analyze numerically the Fokker–Planck equation and compare growth kinetics in the case of noisy (i.e. space-independent) fluctuations. It is shown that for a large class of spatially correlated velocity fluctuations, the growth kinetics is universal, i.e. it does not depend on the details of statistics of f…

Kinetics of Domain Growth and Aging in a Two-Dimensional Off-lattice System

2020

We have used molecular dynamics simulations for a comprehensive study of phase separation in a two-dimensional single component off-lattice model where particles interact through the Lennard-Jones potential. Via state-of-the-art methods we have analyzed simulation data on structure, growth and aging for nonequilibrium evolutions in the model. These data were obtained following quenches of well-equilibrated homogeneous configurations, with density close to the critical value, to various temperatures inside the miscibility gap, having vapor-"liquid" as well as vapor-"solid" coexistence. For the vapor-liquid phase separation we observe that $\ell$, the average domain length, grows with time ($…