A simple and accurate approach for calculating the vibration spectra of molecules on surfaces: Comparisons to high resolution electron energy loss data for ethylene on silicon

Peak assignment is a complex but important task for analyzing the vibration spectra of surface-bound molecules. Here we describe a simple approach for calculating infrared and Raman spectra for surface-bound molecules using a cluster model approach with quantum capping potentials (QCPs). The utility of the approach is demonstrated by comparisons to the measured high resolution electron energy loss spectra for ethylene on clean silicon. By capping the silicon cluster with QCPs we computed spectra that agree very well with the HREEL spectrum, allowing us to easily assign the experimental peaks. QCPs are similar to effective core potentials, can be used with any ab initio technique and most computational chemistry packages, and their use requires no special expertise.     

Quantum states of hydrogen (H, D, T) atoms on Cu(1 0 0) and (1 1 0) surfaces

We investigate the quantum mechanical behavior of adsorbed hydrogen (H, D, T) on Cu(1 0 0) and (1 1 0) surfaces. We construct potential energy surfaces (PESs) for the motion of the hydrogen H atom on Cu(1 0 0) and (1 1 0) surfaces within the framework of density functional theory. The potential energy takes a minimum value on the hollow site of Cu(1 0 0) and on the short bridge site of Cu(1 1 0). Moreover, we calculate the quantum states of hydrogen atom motion on these calculated PESs. The ground state wave function of the hydrogen atom motion is strongly localized around the hollow site on the Cu(1 0 0) surface. On the other hand, the ground state wave function of the hydrogen atom motion on Cu(1 1 0) is distributed from the short bridge site to two neighboring pseudo-threefold sites. We finally show isotope effects on the quantum states of the motion of hydrogen on both surfaces.     

An infrared study of the chemistry of methyl species on Pt(111) formed by the decomposition of dimethylmercury

The chemistry of dimethyl mercury on a Pt(111) single crystal surface has been investigated by reflection-absorption infrared spectroscopy (RAIRS). Dimethyl mercury appears to be highly reactive on Pt(111) and readily decomposes on the surface at temperatures of 100 K and above. Adsorption at 100 K initially occurs in a dissociative manner to produce CH₃ and CH₃Hg species on the surface, both of which are identified as having C_3v local symmetry. At higher exposures, molecular adsorption dominates with the Hg---C---Hg axis initially oriented parallel to the surface. This preferred orientation, however, does not persist into the multilayer. Thermal treatment of the surface layer results in multilayer desorption between 130 and 135 K, and no parent molecular species are observed beyond 160 K. Adsorption at 200 and 300 K produces an overlayer consisting primarily of CH₃Hg species, which are thermally stable to about 350 K. Subsequent heating to 400 K results in the formation of ethylidyne species which are characterised by RAIRS. Adsorption at 400 K results in the direct formation of an ethylidyne layer estimated to be about 85% of saturated coverage.     

Reversible chemisorption of carbon dioxide: simultaneous production of fuel-cell grade H2 and compressed CO2 from synthesis gas

One vision of clean energy for the future is to produce hydrogen from coal in an ultra-clean plant. The conventional route consists of reacting the coal gasification product (after removal of trace impurities) with steam in a water gas shift (WGS) reactor to convert CO to CO₂ and H₂, followed by purification of the effluent gas in a pressure swing adsorption (PSA) unit to produce a high purity hydrogen product. PSA processes can also be designed to produce a CO₂ by-product at ambient pressure. This work proposes a novel concept called “Thermal Swing Sorption Enhanced Reaction (TSSER)” which simultaneously carries out the WGS reaction and the removal of CO₂ from the reaction zone by using a CO₂ chemisorbent in a single unit operation. The concept directly produces a fuel-cell grade H₂ and compressed CO₂ as a by-product gas. Removal of CO₂ from the reaction zone circumvents the equilibrium limitations of the reversible WGS reaction and enhances its forward rate of reaction. Recently measured sorption-desorption characteristics of two novel, reversible CO₂ chemisorbents (K₂CO₃ promoted hydrotalcite and Na₂O promoted alumina) are reviewed and the simulated performance of the proposed TSSER concept using the promoted hydrotalcite as the chemisorbent is reported.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

A concise representation of adsorbate-surface interactions. I. Formulation and model calculation for adsorption of Co on Cu(100) surface

A method is presented to clarify the concepts of the chemisorptive bonds among many chemisorptive interactions. The eigenfunctions of the system are transformed into new orbitals, and the chemisorptive interactions are represented in terms of a few transformed orbitals. To show the usefulness of the present method, the adsorption of CO on the Cu(100) surface is examined within the CNDO/2 approximation. The donation and the type interaction is clearly visualized, and the information of the spatial extent of the chemisorptive interactions is also obtained.     

电场对分子线电子结构的影响

从第一性原理出发,利用密度泛函理论计算了分子2-氨基-5-硝基-1,4-二乙炔基-4-苯硫醇基苯与金原子团形成的分子线的电子结构,从轨道、能级及吸附电子三个方面讨论了电场对分子线电子结构的影响.该工作将有利于未来纳米电子学器件的设计.     

Composite Anderson-Newns model and density of states due to chemisorption: Quasi-chemical approximation

In this paper a variation in density of states (DOS) of the substrate due to chemisorption of hydrogen on transition metals using composite Anderson-Newns model has been investigated for different coverages in quasi-chemical approximation of Fowler and Guggenhiem, which in the limitz→∞ gives the Bragg-Williams approximation as a special case. Variation in density of states has been studied for one-dimensional periodic substrate with change in adatom interaction energy and coverage. With increase in coverage, the bonding and antibonding (B-AB) peaks are found to shift towards higher energies and at the same time relative height of the peaks also increases. The interesting feature to observe is that both approximations for a particular coverage, give split-off states with different height for both (B-AB) peaks. It particularly indicates change in B-AB states, representing amount of chemisorption, with the change in interaction energy between adatoms. At the same time bond strength is also found to decrease with interaction between adatoms.     

Chemisorption on inverse-supported catalysts: H-ZnO/Ni

The chemisorption energy of hydrogen on a semiconductor/metal composite substrate is investigated using the complex-energy-plane integration approach. The electronic properties of the interfacial substrate are described via a Green-function formalism. The tight-binding approximation is employed to model the semiconductor catalysts by a finite chain of alternating s- and p-orbitals, while the semi-infinite metal support is represented by a linear chain of d-orbitals. Specific calculations are performed for the H-ZnO/Ni system.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayAlso the Guelph-Waterloo Program for Graduate Work in Physics     

Adsorption of carbon monoxide Au/Pd(1 0 0) alloys in ultrahigh vacuum: Identification of adsorption sites

The adsorption of carbon monoxide is studied on Au/Pd(1 0 0) alloys by means of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The alloy was formed by adsorbing a four-monolayer thick gold film on a Pd(1 0 0) substrate and by heating to various temperatures to form alloys with a range of palladium coverages. The alloy was characterized using X-ray photoelectron spectroscopy and the composition of the outermost layer measured using low-energy ion scattering spectroscopy. CO adsorbs on palladium bridge sites only for palladium coverages greater than 0.5 monolayers (ML) suggesting that next-nearest neighbor sites are preferentially populated by palladium atoms. CO adsorbs on atop palladium sites and desorbs at ∼350 K corresponding to a desorption activation energy of ∼117 kJ/mol. However, at lower palladium coverages, these sites are not occupied and CO desorption states are detected 170 and 112 K corresponding to desorption activation energies of ∼53 kJ/mol and ∼35 kJ/mol, respectively, for these states. It is suggested that these states are due to a restructuring of the surface to form low-coordination gold sites that obscure the atop palladium site.