Chemisorption phenomena: Analytic modeling based on perturbation theory and bond-order conservation

Tremendous advances in experimental studies of chemisorption revealed that many phenomena could not be understood and projected by the current theoretical constructs. We discuss some of the experimental puzzles that prompted a development of new analytic approaches to chemisorption based on general principles such as perturbation theory (PT) and bond-order conservation (BOC). The PT results concern the periodic regularities of the heat of chemisorption, the role of the antibonding adsorbate orbitals, and universal patterns of adsorbate-induced surface polarization Some of the PT findings are further corroborated within a much broader BOC approach. The BOC model and its postulates (including the use of a Morse potential) and diverse projections are thoroughly discussed. For atomic A and diatomic AB adsorbates, it is shown how the BOC model explicitly and rigorously interrelates a variety of seemingly disparate phenomena such as preferred adsorbate sites, the activation barriers for surface migration and dissociation, relations between atomic Q_A (Q_B) and molecular Q_AB heats of chemisorption, coverage and coadsorption effects on Q_A, overlayer phase transitions and island formation, the nature of promotion and poisoning. The model also projects possible intermediates and elementary steps of surface reactions. Although some of the findings are counter to commonly held perceptions, the whole picture of chemisorption is coherent and fits experiment well. The new conceptual understanding is stressed and some comments on the theory of chemisorption are made.     

Coverage effects under atomic chemisorption: Morse-potential modeling based on bond-order conservation

Our recent analytical Morse-potential model based on bond-order conservation has been extended to treat coverage (θ) effects on the heat of atomic chemisorption Q. For highly symmetric surfaces such as fcc(111), fcc(100), and bcc(100), explicit expressions for Q versus θ have been obtained projecting regularities of Q(θ) and of the overlayer structures, in encouraging agreement with experiment. In particular, the model predicts that Q should typically decrease with θ (though at very low θ, Q can sometimes increase) and that there may be some critical coverage θ_c<1 beyond which the second-order phase transition (hollow→bridge or on-top) will occur.     

Analyses of Ne-diffraction data from transition-metal surfaces based on charge-density calculations

We evaluate the proportionality constant β for neon in the Esbjerg-Nørskov potential V_R(r) = βϱ(r) from experimental data on Ni(110), Ni(113), Cu(110) and Pd(110). Our calculations using overlapping atomic charge densities require that β be material and surface-dependent. Although Ne diffraction is more sensitive to details of corrugation shapes than He, we found it to be insensitive to normal relaxations of the topmost layers.     

Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorption energy of the central, C, N, O, or S atom, the scaling constant depending only on x. A model is proposed to understand this behavior. The scaling model is developed into a general framework for estimating the reaction energies for hydrogenation and dehydrogenation reactions.     

Bond breaking and temporary anion states in uracil and halouracils: implications for the DNA bases

Low energy electrons are capable of breaking bonds in gas phase DNA bases by means of the dissociative electron attachment process. With the aid of new total scattering data in the halouracils and input from quantum chemical calculations, we describe the dipole bound and valence anion states in these compounds and present assignments for the two types of structure appearing in the cross sections. A clear distinction between the two mechanisms for bond breaking is necessary for an understanding of electron induced damage to DNA.     

Theoretical and computational aspects of scattering from rough surfaces: one-dimensional perfectly reflecting surfaces

We discuss the scattering of acoustic or electromagnetic waves from one-dimensional rough surfaces. We restrict the discussion in this report to perfectly reflecting Dirichlet surfaces (TE polarization). The theoretical development is for both infinite and periodic surfaces, the latter equations being derived from the former. We include both derivations for completeness of notation. Several theoretical developments are presented. They are characterized by integral equation solutions for the surface current or normal derivative of the total field. All the equations are discretized to a matrix system and further characterized by the sampling of the rows and columns of the matrix which is accomplished in either coordinate space (C) or spectral space (S). The standard equations are referred to here as CC equations of either the first (CC1) or second kind (CC2). Mixed representation, or SC-type, equations are solved as well as SS equations fully in spectral space.

Computational results are presented for scattering from various periodic surfaces. The results include examples with grazing incidence, a very rough surface and a highly oscillatory surface. The examples vary over a parameter set which includes the geometrical optics regime, physical optics or resonance regime, and a renormalization regime.

The objective of this study was to determine the best computational method for these problems. Briefly, the SC method was the fastest, but it did not converge for large slopes or very rough surfaces for reasons we explain. The SS method was slower and had the same convergence difficulties as SC. The CC methods were extremely slow but always converged. The simplest approach is to try the SC method first. Convergence, when the method works, is very fast. If convergence does not occur with SC, then SS should be used, and failing that CC.     

Theoretical and computational aspects of scattering from rough surfaces: one-dimensional perfectly reflecting surfaces

Abstract

We discuss the scattering of acoustic or electromagnetic waves from one-dimensional rough surfaces. We restrict the discussion in this report to perfectly reflecting Dirichlet surfaces (TE polarization). The theoretical development is for both infinite and periodic surfaces, the latter equations being derived from the former. We include both derivations for completeness of notation. Several theoretical developments are presented. They are characterized by integral equation solutions for the surface current or normal derivative of the total field. All the equations are discretized to a matrix system and further characterized by the sampling of the rows and columns of the matrix which is accomplished in either coordinate space (C) or spectral space (S). The standard equations are referred to here as CC equations of either the first (CC1) or second kind (CC2). Mixed representation, or SC-type, equations are solved as well as SS equations fully in spectral space.

Computational results are presented for scattering from various periodic surfaces. The results include examples with grazing incidence, a very rough surface and a highly oscillatory surface. The examples vary over a parameter set which includes the geometrical optics regime, physical optics or resonance regime, and a renormalization regime.

The objective of this study was to determine the best computational method for these problems. Briefly, the SC method was the fastest, but it did not converge for large slopes or very rough surfaces for reasons we explain. The SS method was slower and had the same convergence difficulties as SC. The CC methods were extremely slow but always converged. The simplest approach is to try the SC method first. Convergence, when the method works, is very fast. If convergence does not occur with SC, then SS should be used, and failing that CC.