Hydrogenation of S to H2S on Pt(111): A first-principles study

Density-functional theory has been used to investigate the chemisorption of S, SH, and H2S as well as the coadsorption of S and H and SH and H on Pt(111). In addition reaction pathways and energy profiles for the conversion of adsorbed S and H into gas-phase H2S have been determined. It has been found that S, SH, and H2S bind preferentially at face-centered-cubic (fcc), bridge, and top sites, respectively. Both the S+H and SH+H reactions have high barriers (similar to1 eV) and high exothermicities (similar to1 eV). This reveals that adsorbed H2S and SH are highly unstable adsorbates on Pt(111) and that adsorbed S (and H) is the most stable SHX (X=0,1,2) intermediate on Pt(111) (C) 2001 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.

General trends in the barriers of catalytic reactions on transition metal surfaces

A catalyst preparation by design is one of the ultimate goals in chemistry. The first step towards this goal is to understand the origin of reaction barriers. In this study, we have investigated several catalytic reactions on some transition metal surfaces, using density functional theory. All the reaction barriers have been determined. By detailed analyses we obtain some insight into the reaction barrier. Each barrier is related to (i) the potential energy surface of reactants on the surface, (ii) the total chemisorption energy of reactants, and (iii) the metal d orbital occupancy and the reactant valency. (C) 2001 American Institute of Physics.

Stepwise addition reactions in ammonia synthesis: A first principles study

Catalytic ammonia synthesis is believed to proceed via dissociation of N-2 and H-2 with subsequent stepwise addition reactions from an adsorbed nitrogen atom to NH3. The first step, N-2 dissociation, has been thoroughly studied. However, little is known about the microscopic details of the stepwise addition reactions. To shed light on these stepwise addition reactions, density functional theory calculations with the generalized gradient approximation are employed to investigate NHx (x=1,3) formation on Ru(0001). Transition states and reaction barriers are determined in each elementary step. It is found that the reaction barriers for stepwise addition reactions are rather high, for example, the barrier for NH hydrogenation is calculated to be 1.28 eV, which is comparable with that of N-2 dissociation. In addition, one of the stepwise addition reactions on a stepped surface is also considered. The reaction barrier is found to be much higher than that of N-2 dissociation on the same stepped surface, which indicates the importance of stepwise addition reactions in ammonia synthesis. (C) 2001 American Institute of Physics.

Insight into electron-mediated reaction mechanisms: Catalytic CO oxidation on a ruthenium surface

Ruthenium is one of the poorest catalysts for CO oxidation under normal conditions (low or medium O coverage and normal temperature). However, a recent study [Science 285, 1042 (1999)] reveals that, under femtosecond laser irradiation, CO2 can be formed on the Ru surface, and the reaction follows an electron-mediated mechanism. We carried out density functional theory calculations to investigate CO oxidation via an electron-mediated mechanism on Ru(0001). By comparison to the reaction under normal conditions, following features emerge in the electron-mediated mechanism: (i) more reaction channels are open; (ii) the reaction barrier is significantly lowered. The physical origins for these novel features have been analyzed. (C) 2001 American Institute of Physics.

CO oxidation on Pd(100) and Pd(111): A comparative study of reaction pathways and reactivity at low and medium coverages

We have performed density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on a close-packed transition metal surface, Pd(lll), and a more open surface, Pd(100), aiming to shed light on surface structure effects on reaction pathways and reactivity, an important issue in catalysis. Reaction pathways on both surfaces at two different coverages have been studied. It is found that the reaction pathways on both surfaces possess crucial common features despite the fact that they have different surface symmetries. Having determined reaction barriers in these systems, we find that the reaction on Pd(lll) is strongly coverage dependent. Surface coverages, however, have little effect on the reaction on Pd(100). Calculations also reveal that the low coverage reactions are structure sensitive while the medium coverage reactions are not. Detailed discussions on these results are given.

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.

The investigation of mechanisms in environmental catalysis using time-resolved methods

The formation of nitrogen oxides (NOx) during a combustion process is difficult to avoid because of the large exotherm and the consequent problem of avoiding local high-temperature spikes. Consequently, for many applications, such as for automotive power generation, there will be a continuing need to use catalytic after-treatment to reduce harmful emissions. The investigation of the mechanisms of the key catalytic reactions in environmental catalysis can provide an insight into the action of the catalyst, and time-resolved methods offer a powerful means to study these processes under realistic conditions. The use of Temporal Analysis of Products (TAP) and Steady State Isotopic Transient Kinetic Analysis (SSITKA) methods to investigate the reduction of NOx under various experimental conditions is described. From a detailed analysis of the SSITKA profiles, it is shown that at low temperatures the mechanism for the formation of N-2 and N2O from NO may differ from the conventional high-temperature mechanism. This is supported by density functional theory calculations, which show that the barrier to the formation of N2O from the reaction of N(ads) and NO(ads) may be too high to allow this process to occur at low temperatures. The alternative reaction of NO(ads) + NO(ads) = N2O(g) + O(ads) is shown to be much more favorable and is consistent with the SSITKA analysis. The remarkable effect of hydrogen as a reductant at low temperatures is described, and alternative interpretations of the role of hydrogen are discussed.

Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

Choline saccharinate and choline acesulfamate: Ionic liquids with low toxicities

Choline saccharinate and choline acesulfamate are two examples of hydrophilic ionic liquids, which can be prepared from easily available starting materials (choline chloride and a non-nutritive sweetener). The (eco)toxicity of these ionic liquids in aqueous solution is very low in comparison to other types of ionic liquids. A general method for the synthesis and purification of hydrophilic ionic liquids is presented. The method consists of a silver-free metathesis reaction, followed by purification of the ionic liquid by ion-exchange chromatography. The crystal structures show a marked difference in hydrogen bonding between the two ionic liquids, although the saccharinate and the acesulfamate anions show structural similarities. The optimized structures, the energetics, and the charge distribution of cation-anion pairs in the ionic liquids were studied by density functional theory (DFT) and second-order (Moller-Plesset) perturbation theory calculations. The occupation of the non-Lewis orbitals was considered to obtain a qualitative picture of the Lewis structures. The calculated interaction energies and the dipole moments for the ion pairs in the gas phase were discussed.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Structural changes in quasi-one-dimensional many-electron systems: From linear to zigzag and beyond

Many-electron systems confined to a quasi-one-dimensional geometry by a cylindrical distribution of positive charge have been investigated by density functional computations in the unrestricted local spin density approximation. Our investigations have been focused on the low-density regime, in which electrons are localized. The results reveal a wide variety of different charge and spin configurations, including linear and zig-zag chains, single-and double-strand helices, and twisted chains of dimers. The spin-spin coupling turns from weakly antiferromagnetic at relatively high density, to weakly ferromagnetic at the lowest densities considered in our computations. The stability of linear chains of localized charge has been investigated by analyzing the radial dependence of the self-consistent potential and by computing the dispersion relation of low-energy harmonic excitations.

Lowest energy potentials of Li2 + F accessible at ultracold temperatures

Ab initio calculations for the strongly exoergic Li2+F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

Spontaneous spin polarization and charge localization in metal nanowires: the role of a geometric constriction

An idealized jellium model of conducting nanowires with a geometric constriction is investigated by density functional theory (DFT) in the local spin density (LSD) approximation. The results reveal a fascinating variety of spin and charge patterns arising in wires of sufficiently low (r(s) >= 15) average electron density, pinned at the indentation by an apparent attractive interaction with the constriction. The spin-resolved frequency-dependent conductivity shows a marked asymmetry in the two spin channels, reflecting the spontaneous spin polarization around the wire neck. The relevance of the computational results is discussed in relation to the so-called 0.7 anomaly found by experiments in the low-frequency conductivity of nanowires at near-breaking conditions (see 2008 J. Phys.: Condens Matter 20, special issue on the 0.7 anomaly). Although our mean-field approach cannot account for the intrinsic many-body effects underlying the 0.7 anomaly, it still provides a diagnostic tool to predict impending transitions in the electronic structure.

Spontaneous spin polarization in geometrically constricted metal nanowires

The electronic structure of thin conducting wires with a narrow geometric constriction has been determined by density-functional theory computations in the local spin density approximation. Spontaneous spin polarization arises in nominally paramagnetic wires at sufficiently low density (r(s)>= 15). Real-space spin-polarization maps show a fascinating variety of magnetic structures pinned at the constriction. The frequency-dependent conductivity is different for the spin-up and spin-down channels and significantly lower than in wires of identically vanishing spin polarization.