Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.     

Fuzzy矩阵方程的摄动问题

讨论了Fuzzy矩阵A的同解简化矩阵A^(2)，指出陈贻源论文《解Fuzzy关系方程》中定量3的错误。研究Fuzzy矩阵方程的摄动问题，解决了汤服成（2000）提出的未解决问题。     

Converged properties of clean metal surfaces by all-electron first-principles calculations

All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties.     

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.     

On the Hyers-Ulam-Rassias stability of functional equations in n-variables

In this paper we investigate a generalization of the Hyers-Ulam-Rassias stability for a functional equation of the form f(φ(X))=?(X)f(X)+ψ(X) and the stability in the sense of Ger for the functional equation of the form f(φ(X))=?(X)f(X), where X lie in n-variables. As a consequence, we obtain a stability result in the sense of Hyers-Ulam-Rassias, Gǎvruta, and Ger for some well-known equations such as the gamma, beta, and G-function type's equations.     

Apparatus for High-Resolution Solid Hydrogen Matrix Isolation Spectroscopy and Its Application

Apparatus integrating a Fourier transform-infrared (FT-IR) spectrometer and a mid-infrared difference frequency generation (DFG) laser spectrometer was built for the study of the matrix isolation spectrum in solid molecular hydrogen. A 3-cm-long molecular hydrogen crystal was grown in a liquid-helium Dewar, and its infrared absorption spectrum in the 1-5 μm region was recorded to test the system. The W₀(0) (ν=0←0, J=6←0) line around 2410 cm⁻¹ of solid hydrogen was investigated with the DFG laser spectroscopy. High-resolution matrix isolation spectrum of CO² co-deposited with hydrogen on a BaF₂ cold plate at liquid-helium temperature was studied.     

A first-principles study of surface and subsurface H on and in Ni(1 1 1): diffusional properties and coverage-dependent behavior

Periodic, self-consistent, density functional theory (GGA-PW91) calculations are performed for both surface and subsurface atomic hydrogen on and in Ni(1 1 1). At a low coverage (θ=0.25 ML), the binding energies (BEs) of a hydrogen atom in surface fcc, subsurface octahedral (first layer), and subsurface octahedral (second layer) sites are −2.89, −2.18, and −2.11 eV, respectively. The activation energy barriers for hydrogen diffusion from the surface to the first subsurface layer and from the first to the second subsurface layer are estimated to be 0.88 and 0.52 eV, respectively. In the entire coverage range studied, hydrogen occupies surface fcc and hcp sites and subsurface octahedral sites. In addition, the magnitude of the BE per hydrogen atom and the magnetization of the nickel slabs both decrease as hydrogen coverage increases. Vibrational frequencies of hydrogen at various surface and subsurface sites are calculated and are in reasonable agreement with experimental data. A phase stability calculation with a 2 × 2 surface unit cell shows that a p(2 × 2)-2H overlayer structure (θ=0.5 ML) and a p(1 × 1)-1H structure (θ=1.0 ML) are stable at low hydrogen pressures, in agreement with numerous experimental results. A very large increase in pressure is required to populate subsurface sites. After such an increase occurs, the first subsurface layer is filled completely.     

HILBERTIAN INVARIANCE PRINCIPLE FOR EMPIRICAL PROCESS ASSOCIATED WITH A MARKOV PROCESS

The authors establish the Hilbertian invariance principle for the empirical process of a stationary Markov process, by extending the forward-backward martingale decomposition of Lyons-Meyer-Zheng to the Hilbert space valued additive functionals associated with general non-reversible Markov processes.     

Nonparametric estimation of distributions with categorical and continuous data

In this paper we consider the problem of estimating an unknown joint distribution which is defined over mixed discrete and continuous variables. A nonparametric kernel approach is proposed with smoothing parameters obtained from the cross-validated minimization of the estimator's integrated squared error. We derive the rate of convergence of the cross-validated smoothing parameters to their ‘benchmark’ optimal values, and we also establish the asymptotic normality of the resulting nonparametric kernel density estimator. Monte Carlo simulations illustrate that the proposed estimator performs substantially better than the conventional nonparametric frequency estimator in a range of settings. The simulations also demonstrate that the proposed approach does not suffer from known limitations of the likelihood cross-validation method which breaks down with commonly used kernels when the continuous variables are drawn from fat-tailed distributions. An empirical application demonstrates that the proposed method can yield superior predictions relative to commonly used parametric models.     

ON MATRIX UNITARILY INVARIANT NORM CONDITION NUMBER

1.IntroductionSince1984,severalchinesemathematicianshaveobtailledmanyresultsboutmatrixoperatornormcondition.umbe.[ll'12'18].Twokindsmatrixconditionnllmbers[9]are:(1)IfAECoxsisnonsingular,thellunlberK.(A)~IIAll.llA--'if.iscalledtheor--normconditionnumberof…