The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

A density functional theory study on the water formation at high coverages and the water effect in the Fischer-Tropsch synthesis

The O removal through water formation is an important process in the Fischer-Tropsch synthesis. In this study, both steps in water formation (O + H --> OH, OH + H --> H2O) are studied on the stepped Co(0001) at high coverages using density functional theory. We find the following. (i) In both O-O and O-OH co-adsorption systems, two transition states (TSs) were located for the O hydrogenation: in one TS, both O and H are on the same terrace, and in the other they are at the interface between the step edge and the terrace below. (ii) In both the O-O and O-OH co-adsorption systems, the O hydrogenation at the interface is easier (E-a = 0.32 eV in the O-O system, E-a = 1.10 eV in the O-OH system) than that on the same terrace (E-a = 1.49 eV in the O-O system, E-a = 1.80 eV in the O-OH system). (iii) In both the O-O and O-OH co-adsorption systems, only one TS for the OH hydrogenation was located, in which both OH and H are on the same terrace. (iv) Compared to the OH hydrogenation in the O-OH system (E-a = 1.46 eV), the reaction in the OH-OH system (E-a = 0.64 eV) is much easier. The barrier differences and the water effect on the Fischer-Tropsch synthesis are discussed. A possible route with low barriers for water formation is proposed.

N2O and NO2 formation on Pt(111): A density functional theory study

Catalytic formation of N2O and NO2 were studied employing density functional theory with generalized gradient approximations, in order to investigate the microscopic reaction pathways of these catalytic processes on a Pt(111) surface. Transition states and reaction barriers for the addition of chemisorbed N or chemisorbed O to NO(ads) producing N2O and NO2, respectively, were calculated. The N2O transition state involves bond formation across the hcp hollow site with an associated reaction barrier of 1.78 eV. NO2 formation favors a fcc hollow site transition state with a barrier of 1.52 eV. The mechanisms for both reactions are compared to CO oxidation on the same surface. The activation of the chemisorbed NO and the chemisorbed N or O from the energetically stable initial state to the transition state are both significant contributors to the overall reaction barrier E-a, in contrast to CO oxidation in which the activation of the O-(ads) is much greater than CO(ads) activation. (C) 2002 American Institute of Physics.

Methane transformation to carbon and hydrogen on Pd(100): Pathways and energetics from density functional theory calculations

Density functional theory with gradient corrections has been employed to study the reaction pathways and the reaction energetics for the transformations of CH4 to C and H on a Pd(100) surface. On examination of transition state structures identified in each elementary reaction, a clear relationship between the valencies of the CHx fragments and the locations of the transition states emerges. The higher the valency of the CHx fragment, the higher the coordination number of the CHx with the surface atoms. The calculated reaction energetics are in good agreement with the experiments. In addition, calculation results are also used to illustrate an interesting issue concerning the CH3 stability on Pd surfaces. (C) 2002 American Institute of Physics.

A first principles study of methanol decomposition on Pd(111): Mechanisms for O-H bond scission and C-O bond scission

There is some dispute as to whether methanol decomposition occurs by O-H bond scission or C-O bond scission. By carrying out density functional theory calculations, we investigate both scenario of the reaction pathways of methanol decomposition on a Pd(111) surface. It is shown that the O-H bond scission pathway is much more energetically favorable than the C-O bond scission pathway. The high reaction barrier in the latter case is found to be due to the poor bonding abilities of CH3 and OH with the surface at the reaction sites. (C) 2001 American Institute of Physics.

A density functional theory study of the reaction of C+O, C+N, and C+H on close packed metal surfaces

Density functional theory (DFT) has been used to determine reaction pathways for several reactions taking place on Pt(111) and Cu(111) surfaces. On Pt(111), the reactions of C+O and C+N were studied, and on Cu(111) we investigated the reaction of C+H. The structures of the transition states accessed in each reaction are similar. An equivalent distance separates the reactants with the first located at a three-fold hollow site and the second close to a bridge site. Previous DFT studies have, in fact, often identified transition states of this type and in every case it is the reactant with the weaker chemisorption energy that is located close to the bridge site. An explanation as to why this is so is provided. (C) 2001 American Institute of Physics.

Softened C-H modes of adsorbed methyl and their implications for dehydrogenation: An ab initio study

To investigate the softening of CH vibrational frequencies and their implications for dehydrogenation of adsorbed hydrocarbons, an issue of scientific and technological importance, density functional theory calculations have been performed on the chemisorption and dehydrogenation of CH3 on Cu(111) and Pt(111) surfaces. By comparing these results with those of Ni(111) we find that the CH bonds of the adsorbate, when close enough, interact with metal atoms of the surface. It is this interaction and its associated lengthening and weakening of CH bonds that is the physical origin of mode softening. We rule out the possibility of a relationship between the mere presence of mode softening and dehydrogenation. We do show, however, that there is a clear relationship between the extent to which a surface can induce mode softening and the activation energy to dehydrogenation. In addition, periodic trends concerning the extent of mode softening are reproduced. (C) 2001 American Institute of Physics.

Dynamic resonances and tunnelling in the multiphoton ionization of argon

We present results of wavepacket simulations for multiphoton ionization in argon. A single active electron model is applied to estimate the single-electron ionization rates and photoelectron energy distributions for lambda = 390 nm light with intensities up to I = 2 x 10(14) W cm(-2). The multiphoton ionization rates are compared with R-matrix Floquet calculations and found to be in very good agreement. The photoelectron energy distribution is used to study the nature of ionization at the higher intensities. Our results are consistent with recent calculations and experiments which show the imprint of the tunnelling process in the multiphoton regime. For few-cycle intense pulses, we find that the strong modulation of intensity and increased bandwidth leads to dynamic mixing of the 3d and 5s resonances.

Potential and kinetic sputtering of alkanethiol self-assembled monolayers by impact of highly charged ions

Highly charged ions have been used to study the sputtering of positive molecular fragments from mercaptoundecanoic acid and dodecanethiol self-assembled monolayers on gold surfaces. The samples were bombarded with Arq+ (42n⁺, and Cn+1O2H_{2n + 1}⁺ from mercaptoundecanoic and H+, CnH_2n⁺, and Cn+1H_{2n + 3}⁺ from dodecanethiol. The proton yields were increased with larger charge state q of the highly charged ion (HCI) in both samples, scaling as qgamma, with gamma~5. The charge state dependence is discussed in terms of electron transfer to the HCI. The final yield of protons depends on molecular functional group characteristics, orientation on the surface, and reneutralization phenomena.

Compact ridge waveguide filter with parallel and series-coupled resonators

A novel 3rd-order compact E-plane ridge waveguide filter is presented. Miniaturization is achieved upon introducing a configuration of parallel-coupled E-plane ridge waveguide resonators. Furthermore, the proposed filter allows for transmission zeros at finite frequencies. Fabrication simplicity and mass producibility of standard E-plane filters is maintained. The numerical and experimental results are presented to validate the proposed configuration. A miniaturisation factor of 2 and very sharp upper cutoff are achieved. 2005 Wiley Periodicals, Inc.

Compact ridged-waveguide bandpass filters and diplexers

A ridged-waveguide diplexer incorporating integrated compact ridged-waveguide filters and a ridged-waveguide T-junction is presented. The compact size of the filter is achieved by integrating of bandpass periodic filter, and a low-pass structure is used in order to suppress spurious responses. Simulation using the mode-matching method has been carried out for ridge-waveguide filters and T junctions and the results are presented. The measured results are in good agreement with the simulated results. (C) 2004 Wiley Periodicals, Inc.

Crystal structure and ab initio calculations of a cyano-carbamimidic acid ethyl ester

The structure of one tautomer (amine form) of cyano-carbamimidic acid ethyl ester or (amino-ethoxy-methylidene)aminoformonitrile (CAS: 13947-84-7) was determined by single crystal X-ray diffraction. Ab initio quantum chemical calculations at the B3LYP, MP2 and G3 levels were performed to investigate the stability and the formation of the different tautomers and conformers. The calculations indicate that the amine form is the more stable tautomer, showing a high degree of election conjugation. The most stable amine conformer located by the calculations corresponds to the crystallized structure. On the contrary, in the less stable imine form, the conjugation is separated by a N2-C2 single bond. (C) 2007 Elsevier B.V. All rights reserved.

The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies

The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/ or increasing the concentration of dissolved O-2 reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (COL) and three-fold hollow bonded CO (COH) adsorbates were produced following CO adsorption at Ru(0001) in H2SO4, as was observed in our previous studies in HClO4. However, the amount of adsorbed CO observed in H2SO4 was ca. 10% less than that in HClO4; in addition, the COL and COH frequencies were higher in H2SO4, and the onset potential for COads oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H2SO4 compared both to the data under potential control and to our earlier data in HClO4, and these observations were rationalized in terms of the adsorbed HSO4- anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O-2. Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H2SO4 supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential implications with respect to fuel cell electrocatalysis.