Interfacial segregation in Ag-Au,Au-Pd,and Cu-Ni alloys: I. (100) surfaces

Atomistic simulations of segregation to (100) free surface in Ag–Au, Au–Pd, and Cu–Ni alloy systems have been performed for a wide range of temperatures and compositions within the solid solution region of these alloy phase diagrams. In addition to the surface segregation profiles, surface free energies, enthalpies, and entropies were determined. These simulations were performed within the framework of the free energy simulation method, in which an approximate free energy functional is minimized with respect to atomic coordinates and atomic site occupation. The effects of the relaxation with respect to either the atomic positions or the atomic concentrations are discussed. For all alloy bulk compositions (0.05 C 0.95) and temperatures (400 T(K) 1,100) examined, Ag, Au, and Cu segregates to the surface in the Ag–Au, Au–Pd, and Cu–Ni alloy systems, respectively. The present results are compared with several theories for segregation. The resultant segregation profiles in Au–Pd and Ag–Au alloys are shown to be in good agreement with an empirical segregation theory, while in Cu–Ni alloys the disagreement in Ni-rich alloys is substantial. The width of the segregation profile is limited to approximately three to four atomic planes. The surface thermodynamic properties depend sensitively on the magnitude of the surface segregation, and some of them are shown to vary linearly with the magnitude of the surface segregation.     

Environment of the P b center at the Si(111)/oxide interface

We assess several models for the environment of the P _b center (Si dangling bond center) at the interface of Si(111) with its oxide. The comparison of hyperfine constants observed with those predicted using large cluster models favors a local structure in which there is an Si-Si bond within the oxide close to the Si dangling bond. Such Si-Si bonds are also suggested by a number of other experiments and are consistent with the reactive layer model proposed to rationalize a range of oxidation studies.     

On the Landau-Teller approximation for energy exchanges with fast degrees of freedom

We revisit the Landau-Teller heuristic approach to adiabatic invariants and, following Rapp, use it to investigate the energy exchanges between the different degrees of freedom, in simple Hamiltonian systems describing the collision of fast rotating or vibrating molecules with a fixed wall. We critically compare the theoretical results with particularly accurate numerical computations (quite small energy exchanges, namely of one part over 10³⁰, are measured).     

Langevin dynamic simulation of hysteresis in a field-swept Landau potential

Numerical simulations are done of Langevin dynamics for a uniform-orderparameter, field-swept Landau model,= –|a/2|m ²+|b/4|m ⁴–mh(t) , to study hysteresis effects. The field is swept at a constant rateh(t)=h(0)+ht. The stochastic jump values of the field {h_J from an initially prepared metastable minimumm(0) are recorded, on passage to a global minimum m(). The results are: (a) The mean jump¯h _J(h) increases (hysteresis loop widens) with h, confirming a previous theoretical criterion based on rate competition between field-sweep and inverse mean first-passage time (FPT); (b) The broad jump distribution(h _J,h) is related to intrinsically large FPT fluctuations ( ²–²)/ ² O(1), and can be quantitatively understood. Possible experimental tests of the ideas are indicated.     

Synthesis of Diethyl Oxalate by a Coupling-Regeneration Reaction of Carbon Monoxide

This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.     

Surface tension and universality in the three-dimensional Ising model

The amplitude ₀ of the interfacial free energy per unit area (or surface tension) of the body-centered-cubic Ising model is found using a direct monte carlo simulation technique. The combination ²/k_BT_c, where is the correlation length, is shown to agree within the precision of the simulations with a previously reported estimate for the simple cubic lattice. Evidence is also presented for the universality of the finite-size scaling amplitude for the surface tension.     

COMPUTER SIMULATION OF A SINGLE POLYMER CHAIN IN DIFFERENT SOLVENTS

In the present paper, the behavior of a single polymer chain under various solvent conditions was modeled by self-avoiding walks (SAW) with nearest neighbors attraction Δε on a simple cubic lattice. Determination of the θ-condition wasbased on the numerical results of the mean square radius of gyration and end-to-end distance. It was found that at the θtemperatue Δε/kT equals -0.27. The exponents a in the Mark-Houwink equation with different interaction parameters areconsistent with the results of experiments: under θ-condition, a = 0.5, and for a good solvent α= 0.74-0.84, respectively.     

Multistep electrochemical reactions involving transport of intermediates between the near-electrode layer and the bulk solution: A kinetics analysis based on theory of generalized variables (theory of similarity)

A kinetic analysis of multistep electrochemical reactions involving partial diffusion transport of intermediates between the near-electrode layer and the bulk electrolyte is performed within theory of generalized variables (theory of similarity). Dimensionless complexes (similarity criteria) that characterize such reactions are obtained, and their values corresponding to the transport of intermediates are determined.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 121–125.Original Russian Text Copyright © 2005 by Protsenko, Danilov.     

Molecular dynamics simulations of conserved Hox protein hexapeptides. I. Folding behavior in water solution

Molecular dynamics simulations of hexapeptides TFDWMK and LFPWMR; the highly conserved regions of Hox proteins Hox B1 and Hox B8, respectively, are carried out starting from extended structures to investigate their conformational space in water solution. In addition, we have studied TADWMK and TADAMK, where the aromatic residues Phenylalanine and Tryptophan were successively substituted for Alanine to investigate effects from the presence/absence of aromatic amino acids and interactions between them to folding behavior. The backbone of the hexapeptides in all simulations folds to a similar conformation found in experimental studies in solution. Intramolecular, hydrophobically driven interactions between the aromatic residues and internal hydrogen bonds are found to stabilize the conformations.     

Partial Molar Volumes and Partial Molar Adiabatic Compressibilities of Fe(III) Tetrafluoroborate Complexes with DMSO, Pyridine, and Pyridine Derivatives

The apparent and limiting apparent molar volumes of dilute aqueous solutions of KBF₄, and the complexes [Fe(DMSO)₆](BF₄)₃, [Fe(Py)₄(H₂O)₂](BF₄)₃, [Fe(4-Mepy)₂(H₂O)₂](BF₄)₃, and [Fe(4-Etpy)₂(H₂O)₂](BF₄)₃ were determined from density data measured at 5, 15, and 25°C. The apparent and limiting apparent molar adiabatic compressibilities of these complexes were determined from ultrasonic sound velocities measured at the same temperatures in dilute aqueous solutions. The volume change associated with complex formation is discussed in terms of the nature of the coordinate bond and also the role of the central metal atom and ligands in the solvation behavior of these complexes.