Search results for "Statistical"
showing 10 items of 4960 documents
Toward a density functional description of liquid pH2.
2010
A finite-temperature density functional approach to describe the properties of parahydrogen in the liquid-vapor coexistence region is presented. The first proposed functional is zero-range, where the density-gradient term is adjusted so as to reproduce the surface tension of the liquid-vapor interface at low temperature. The second functional is finite-range and, while it is fitted to reproduce bulk pH2 properties only, it is shown to yield surface properties in good agreement with experiments. These functionals are used to study the surface thickness of the liquid-vapor interface, the wetting transition of parahydrogen on a planar Rb model surface, and homogeneous cavitation in bulk liquid…
Reaction coordinates and transition states in enzymatic catalysis
2017
Enzymatic reactions are complex chemical processes taking place in complex dynamic environments. Theoretical characterization of these reactions requires the determination of the reaction coordinate and the transition state ensemble. This is not an easy task because many degrees of freedom may be involved in principle. We present recent efforts to find good enzymatic reaction coordinates and the implications of these findings in the interpretation of enzymatic efficiency. In particular, we analyze different strategies based on the use of minimum free energy paths and direct localization of the dividing surface on multidimensional free energy surfaces. Another strategy is based on the genera…
An empirical model for free surface energy of strained solids at different temperature regimes.
2006
Abstract We have developed an empirical formulation, based on the elastic theory, to calculate the variation of the surface free energy when a crystal is strained in the elastic regime. The model permits to obtain the variation of the surface energy at different strains and temperatures when are known the thermal dependence on the bulk and surface elastic constants. Molecular dynamics (MD) simulations were performed using the three low index surfaces of Al, to validate the accuracy of the model. The comparison between the empirical model and the MD simulations shows a good agreement for temperatures ranging between 0 and 900 K, and for deformation between −2% and 2%.
Digit replacement: A generic map for nonlinear dynamical systems
2016
A simple discontinuous map is proposed as a generic model for nonlinear dynamical systems. The orbit of the map admits exact solutions for wide regions in parameter space and the method employed (digit manipulation) allows the mathematical design of useful signals, such as regular or aperiodic oscillations with specific waveforms, the construction of complex attractors with nontrivial properties as well as the coexistence of different basins of attraction in phase space with different qualitative properties. A detailed analysis of the dynamical behavior of the map suggests how the latter can be used in the modeling of complex nonlinear dynamics including, e.g., aperiodic nonchaotic attracto…
Structure and Dynamics of the Instantaneous Water/Vapor Interface Revisited by Path-Integral and Ab Initio Molecular Dynamics Simulations
2015
The structure and dynamics of the water/vapor interface is revisited by means of path-integral and second-generation Car-Parrinello ab-initio molecular dynamics simulations in conjunction with an instantaneous surface definition [A. P. Willard and D. Chandler, J. Phys. Chem. B 114, 1954 (2010)]. In agreement with previous studies, we find that one of the OH bonds of the water molecules in the topmost layer is pointing out of the water into the vapor phase, while the orientation of the underlying layer is reversed. Therebetween, an additional water layer is detected, where the molecules are aligned parallel to the instantaneous water surface.
Detecting self-similarity in surface microstructures
2000
The relative configurational entropy per cell as a function of length scale is a sensitive detector of spatial self-similarity. For Sierpinski carpets the equally separated peaks of the above function appear at the length scales that depend on the kind of the carpet. These peaks point to the presence of self-similarity even for randomly perturbed initial fractal sets. This is also demonstrated for the model population of particles diffusing over the surface considered by Van Siclen, Phys. Rev. E 56 (1997) 5211. These results allow the subtle self-similarity traces to be explored.
Surface-directed spinodal decomposition: modelling and numerical simulations
1997
We critically review the modelling and simulations of surface-directed spinodal decomposition, namely, the dynamics of phase separation of a critical or near-critical binary mixture in the presence of a surface with a preferential attraction for one of the components of the mixture.
Roughening of the Cu(110) surface
1993
The structure of the Cu(110) surface is studied at high temperatures using a combination of lattice-gas Monte Carlo and molecular dynamics methods with identical many-atom interactions derived from the effective medium theory. The anisotropic six-vertex model is used in the interpretation of the lattice-gas results. We find a clear roughening transition around T_R=1000K and T_R/T_M=0.81. Molecular dynamics reveals the clustering of surface defects as the atomistic mechanism of the transition and allows us to estimate characteristic time scales. For the system of size 50x50, the time scale of the local roughening at 1150 K of an initially smooth surface is of the order of 100 ps.
Numerical and theoretical considerations on the surface energy for pure solids under strain
2004
In this paper we developed a numerical analysis, by means of molecular dynamics (MD) simulations, for the surface energy of solids when a stress is applied parallel to the surface. Our MD simulations for Al showed that under these conditions; compression or an alternation of compression and tension, with respect to the bulk, of some atomic layers below the surface is present. Moreover, we quantified the surface energy variations that led us to propose an empirical model.
Thermodynamics of Nanoparticles: Experimental Protocol Based on a Comprehensive Ginzburg-Landau Interpretation
2014
MATERIAUX+SMR:SDA; The effects of surface and interface on the thermodynamics of small particles require a deeper understanding. This step is crucial for the development of models that can be used for decision-making support to design nanomaterials with original properties. On the basis of experimental results for phase transitions in compressed ZnO nanoparticles, we show the limitations of classical thermodynamics approaches (Gibbs and Landau). We develop a new model based on the Ginzburg-Landau theory that requires the consideration of several terms, such as the interaction between nanoparticles, pressure gradients, defect density, and so on. This phenomenological approach sheds light on …