Hydrogenation mechanism in lanthanum-activated magnesium films

With density-functional theory, the dissociative chemisorptions and diffusion processes of hydrogen on both pure and La-doped Mg(0001) surfaces are studied. Calculation results show that the energy barrier obtained for hydrogen dissociation on the La-doped Mg(0001) surface is smaller due to back-donated bonding between molecular H₂ and doped La atom. The obtained diffusion barriers (0.8–0.22 eV) imply a fast motion of atomic H on La-doped Mg(0001) surface.     

Theoretical study of hydrogen dissociation and diffusion on Nb and Ni co-doped Mg(0001): A synergistic effect

The interaction of H₂ with clean, Ni and Nb doped Mg(0001) surface are investigated by first-principles calculations. Individual Ni and Nb atoms within the outermost surface can reduce the dissociation barrier of the hydrogen molecule. They, however, prefers to substitute for the Mg atoms within the second layer, leading to a weaker catalytic effect for the dissociation of H₂, a bottleneck for the hydriding of MgH₂. Interestingly, co-doping of Ni and Nb stabilizes Ni at the first layer, and results in a significant reduction of the dissociation barrier of H₂ on the Mg surface, coupled with an increase of the diffusion barrier of H. Although codoped Ni and Nb shows no remarkable advantage over single Nb here, it implies that the catalytic effect could be optimized by co-doping of “modest” transition metals with balanced barriers for dissociation of H₂ and diffusion of H on Mg surfaces.     

过渡族金属掺杂Al(111)表面对氢分子催化分解的影响

为了探求过渡金属催化剂对催化合成储氢材料NaAlH₄效果的影响, 本文采用第一性原理方法研究了多种金属原子取代Al (111)表面铝原子形成的合金表面对氢的催化分解的影响. 计算结果表明, Sc, V, Fe, Ti原子掺杂的表面对氢分子分解具有催化作用. H₂在对应的掺杂表面催化分解所需要的活化能分别为0.54 eV, 0.29 eV, 0.51 eV, 0.12 eV. H原子在Sc, V, Ti掺杂表面扩散需要的活化能分别为0.51 eV, 0.66 eV, 0.57 eV. 同时, 过渡金属掺杂在Al表面时倾向于分散分布, 增加掺杂表面的掺杂原子个数, 掺杂表面的催化效果体现为单个掺杂过渡金属原子的催化效果. 本研究将为金属掺杂Al (111)表面催化加氢合成NaAlH₄提供理论参考.     

Dissociations of O2 molecules on ultrathin Pb(111) films: first-principles plane wave calculations

Using first-principles calculations, we systematically study the dissociations of O₂ molecules on different ultrathin Pb(111) films. According to our previous work revealing the molecular adsorption precursor states for O₂, we further explore why there are two nearly degenerate adsorption states on Pb(111) ultrathin films, but no precursor adsorption states existing at all on Mg(0001) and Al(111) surfaces. The reason is concluded to be the different surface electronic structures. For the O₂ dissociation, we consider both the reaction channels from gas-like and molecularly adsorbed O₂ molecules. We find that the energy barrier for O₂ dissociation from the molecular adsorption precursor states is always smaller than that from O₂ gas. The most energetically favorable dissociation process is found to be the same on different Pb(111) films, and the energy barriers are found to be influenced by the quantum size effects of Pb(111) films.     

Density functional theory study of hydrogenation mechanism in Fe-doped Mg(0 0 0 1) surface

Using density functional theory (DFT) in combination with nudged elastic band (NEB) method, the dissociative chemisorptions and diffusion processes of hydrogen on both pure and Fe-doped Mg(0 0 0 1) surfaces are studied. Firstly, the dissociation pathway of H₂ and the relative barrier were investigated. The calculated dissociation barrier (1.08 eV) of hydrogen molecule on a pure Mg(0 0 0 1) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0 0 0 1) surface, the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe. Then, the diffusion processes of atomic hydrogen on pure and Fe-doped Mg(0 0 0 1) are presented. The obtained diffusion barrier to the first subsurface is 0.45 eV and 0.98 eV, respectively. Finally, Chou method was used to investigate the hydrogen sorption kinetic mechanism of pure MgH₂ and Mg mixed with 5 at.% Fe atoms composites. The obtained activation energies are 0.87 ± 0.02 and 0.31 ± 0.01 eV for H₂ dissociation on the pure surface and H atom diffusion in Fe-doped Mg surfaces, respectively. It suggests that the rate-controlling step is dissociation of H₂ on the pure Mg surface while it is diffusion of H atom in the Fe-doped Mg surface. And both of fitting data are matching well with our calculation results.     

In在Al(001)表面偏析的模拟

通过一种空位模型详细的描述了In在Al(001)表面的扩散偏析过程,利用周期性密度泛函理论方法计算了这个偏析过程中每步构型的能量和In原子扩散的能量壁垒,并对可能的偏析机理进行分析.结果表明:In原子从Al(001)表面第二层扩散偏析至表面层时,系统的能量降低了0.64 eV,最大的扩散迁移壁垒为0.34 eV;而从表面更内层向表面第二层扩散时系统能量基本保持不变,扩散需要克服的能量壁垒为0.65 eV,说明In原子在Al(001)表面只能由体内向表面扩散偏析.In在Al(001)的清洁表面具有强烈的偏析趋势,在热力学上是容易进行的. 关键词： 密度泛函理论 表面偏析 扩散 Al合金     

Rotation of hydrogen molecules during the dissociative adsorption on the Mg(0001) surface: a first-principles study

Using first-principles calculations,we systematically study the potential energy surfaces and dissociation processes of the hydrogen molecule on the Mg(0001) surface.It is found that during the dissociative adsorption process with the minimum energy barrier,the hydrogen molecule first orients perpendicularly,and then rotates tobecome parallel to the surface.It is also found that the orientation of the hydrogen molecule in the transition state is neither perpendicular nor parallel to the surface.Most importantly,we find that the rotation causes a reduction of the calculated dissociation energy barrier for the hydrogen molecule.The underlying electronic mechanism for the rotation of the hydrogen molecule is also discussed in the paper.     

Interaction of water with stepped Co(0001): how is it different from flat Co(0001)?

The adsorption and dissociation of water monomer and dimer on stepped Co(0001) surface were studied by means of first-principles calculations. Present results indicate that the adsorption strength of water is greatly enhanced by the presence of step, while the activity of water monomer dissociation does not exhibit a noticeable improvement. Nevertheless, water dimer partial dissociation on stepped Co(0001) is more active than on flat Co(0001), and the promotion of oxygen atom on O–H bond cleavage of H₂O is more prominent on stepped surface than on flat Co(0001). The findings reveal the importance of low coordinated surface atoms on metallic catalysts and the vital role of surface rippling on water dissociation. Together with previous reports, the activity of water dissociation on cobalt-based catalytic surfaces depends dominantly on O-containing species like oxygen atom, H₂O or hydroxyl.     

Ab initio determination of atomic structure and energy of surface states of bare and hydrogen covered GaN (0001) surface — Existence of the Surface States Stark Effect (SSSE)

Density Functional Theory (DFT) calculations indicate that energetically stable structure of clean GaN(0001) surface posses (2 × 1) reconstruction, having every second row of Ga located near plane of N atoms, that gives rise to Ga-related dispersionless surface electronic state, already identified by angle resolved photoelectron spectroscopy (ARPES) measurements [S.S. Dhesi et al. Phys. Rev. B 56 (1997) 10271, L. Plucinski et al. Surf. Sci 507-10 (2002) 223, S. M. Widstrand et al. Surf. Sci. 584 (2005) 169]. The energy reduction in reconstruction proceeds via change of the hybridization of the occupied Ga surface states from sp³ to sp², transforming the empty states to p_z type. It is also shown that the electric subsurface field, modeled in new slab model which allows to simulate electric fields at the semiconductor surfaces [P. Kempisty et al., J. Appl. Phys. 106 (2009) 054901], strongly affects the energy of electronic states of GaN(0001) surfaces. The change of the field may shift the energy of surface states of bare and hydrogen covered GaN(0001) surface, by several eV with respect to the band states. The phenomenon, denoted as Surface States Stark Effect (SSSE), explains various band bending values, measured at differently doped n-type GaN(0001) surfaces. It is shown also that, for the adsorbate density up to one H atom for each Ga surface atom i.e. 1 monolayer coverage (1 ML), the hydrogen adatoms are located at the on-top positions, i.e. directly above Ga atoms. For these adsorbate densities, the H-related quantum surface state is located slightly below the valence band maximum (VBM) in the case of p-type GaN surface. For n-type GaN, the H-related surface state is located deeply in the valence band, about 2 eV below VBM. For higher, 1.25 ML hydrogen coverage, the two H adatoms create either surface attached H₂ ad-molecule (energetically stable) or triple bridge configuration is created (metastable). The H₂ ad-molecule is weekly attached to the surface, having the desorption energy barrier equal to 0.16 eV. For 1.25 ML coverage the DFT results were obtained for p-type GaN only. They show that in the ad-molecule case, a new surface electronic state arises which is located about 6.7 eV below VBM. In the case of the bridge configuration, the bridge related surface state is located closely to the conduction band minimum (CBM).     

First principles study of oxygen adsorption on nickel-doped graphite

Density functional theory is used in a spin-polarized plane wave pseudopotential implementation to investigate molecular oxygen adsorption and dissociation on graphite and nickel-doped graphite surfaces. Molecular oxygen physisorbs on graphite surface retaining its magnetic property. The calculated adsorption energy is consistent with the experimental value of ?0.1?eV. It is found that substituting a carbon atom of the graphite surface by a single doping nickel atom (2.8% content) makes the surface active for oxygen chemisorption. It is found that the molecular oxygen never adsorbs on doping nickel atom while it adsorbs and dissociates spontaneously into atomic oxygens on the carbon atoms which are bound to the nickel. The adsorption energy of ?1.4?eV and zero activation energy barrier indicate that O₂ dissociative adsorption is both thermodynamically and kinetically favoured over the surface. The large electric field near the doping nickel atom along with the excess electrons on the neighbouring carbon atoms, which are bound to the nickel induce molecular oxygen to adsorb and dissociate favourably.     

Liénard-type chemical oscillator

Using first-principles calculation, we have studied the properties of a series of M _x Co_1?x /Co(0001) (M = Pd, Pt) bimetallic surface alloys with atom M ratios from 0.25 to 1.0, then the effect of alloyed M metal on the properties of S adsorbed on these surfaces are discussed. Our calculations show that the alloying of metal Pd, Pt on Co(0001) weakens the S-M (M = Pd, Pt, Co) bond strength compared to monometallic surfaces and the site preference of sulfur atom is dependent on the alloyed metal M and its surface concentration. Moreover, bimetallic surface electronic structure modifications with and without sulfur are analyzed in comparison with clean Co(0001), and the correlation between the sulfur adsorption energy and the bimetallic surface d-band center is presented.     

Polarization and charge transfer during the dissociation of H2 on Al(110)

We present a density functional calculation within the generalized gradient approximation of the H₂ induced dipole moment along the reaction path for dissociation outside an Al(110) surface. The dipole moment is found to change sign during the adsorption process, being positive far from the surface and negative closer in where the antibonding H₂ level is being filled. Assuming this variation to be qualitatively similar for other surfaces, we can classify the effect of an electrostatic field or an adsorbed alkali atom on the adsorption process according to whether the barrier to adsorption is in the entrance channel or the exit channel. The electrostatic interaction model is shown to qualitatively explain why adsorbed alkalies promote the dissociation of     

The effect of defects on the hydrogenation in Mg (0 0 0 1) surface

Density-functional theory was presented to investigate the hydrogen dissociation on a pure, Pt-doped, vacancy and oxide Mg(0 0 0 1) surface. Our results show that the energy barriers are 1.05, 0.39, 0.93 and 1.33 eV for H₂ dissociation on the pure, Pt-doped, vacancy and oxide Mg surface, respectively. The calculation results imply that the initial dissociation of H₂ is enhanced significantly for the Pt-doped Mg(0 0 0 1) surface, negligible for the vacancy model and weekend for the oxide model. The density of state results shows that, following the dissociation reaction coordinate, the H–H interactions are weeker for the Pt-doped model while interactions become stronger for the oxide model. It is suggested that the dissociation process is facilitated when Pt atom acts as catalyst and oxide overlayers delay hydrogen adsorption on the Mg layer. The present study will help us understand the defect role being played for the improvement or opposition effect in absorption kinetics of H₂ on the Mg(0 0 0 1) surface.     

The mechanism of H2 dissociation and adsorption on Mn-modified Ni(111) surface: A density functional theory-based investigation

The mechanism of H₂ dissociative adsorption on Mn-modified Ni(111) surface is investigated and explained using spin-polarized density functional theory (DFT). Potential energy surface (PES) is used to determine the efficient reaction pathway of H₂ on the surface. The dissociative adsorption of H₂ in the hollow sites with its center-of-mass (CM) positioned on top of Ni atom has low activation barrier. This is lower compared if its CM is on top of the Mn atom. The difference in the reactivity of H₂ with Ni and Mn as the CM is corroborated by the positions of the bonding and antibonding orbitals of H₂ as it approaches the surface which is verified from local density of states (LDOS). The greater density of states in the region around the Fermi level of the d_zz, d_xz, and d_yz orbitals of the Ni atom explains the low activation barrier obtained for the dissociation of H₂ on top of the Ni atom in the Mn-modified Ni(111) surface.     

Adsorption and diffusion of H2O molecule on the Be(0001) surface: A density-functional theory study

Using first-principles calculations, we systematically study the adsorption behavior of a single molecular H₂O on the Be(0001) surface. We find that the favored molecular adsorption site is the top site with an adsorption energy of about 0.3 eV, together with the detailed electronic structure analysis, suggesting a weak binding strength of the H₂O/Be(0001) surface. The adsorption interaction is mainly contributed by the overlapping between the s and pz states of the top-layer Be atom and the molecular orbitals 1b₁ and 3a₁ of H₂O. The activation energy for H₂O diffusion on the surface is about 0.3 eV. Meanwhile, our study indicates that no dissociation state exists for the H₂O/Be(0001) surface.     

Adsorption of H2O on clean and on boron-contaminated Rh surfaces

The adsorption and dissociation of H₂O on Rh(111) and Rh foil surfaces have been studied in UHV using Auger electron, electron energy loss (in the electronic range) and thermal desorption spectroscopy. H₂O adsorbs weakly on clean Rh samples at 110 K. The adsorption is accompanied by the appearance of a broad loss feature at 14–14.5 eV. At higher exposures new losses appeared at 8.6 and 10.5 eV. The desorption of H₂O took place in two stages, with T_p = 183 K (β, chemisorption) and 158 K (α, multilayer formation). There was no indication of dissociation of H₂O on a clean Rh(111) surface. Similar results were obtained for a clean Rh foil. However, when small amounts of boron segregated on the surface of Rh, they exerted a dramatic influence on the adsorptive properties of this surface and caused the dissociation of H₂O. This was exhibited by the formation of H₂, by the buildup of surface oxygen, by the appearance of an intense new loss at 9.4 eV, identified as B-O surface species, and by the development of “boron-oxide”-like Auger fine structure.     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.     

Asymmetry in electrical properties of Al‐doped TiO2 film with respect to bias voltage

The energy diagram of RuO₂/Al‐doped TiO₂/RuO₂ structures was estimated from the capacitance–voltage and leakage current density–voltage curves. The Al‐doping profile in TiO₂ film was varied by changing position of the atomic layer deposition cycle of Al₂O₃ during the atomic layer deposition of 9 nm‐thick TiO₂ film. The interface between the TiO₂ film and the RuO₂ electrode containing Al‐doping layer showed a higher Schottky barrier by 0.1 eV compared with the opposite interface without the doping layer. The evolution of various leakage current profiles upon increasing the bias with opposite polarity could be well explained by the asymmetric Schottky barrier. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Dissociation of hydrogen molecules on the clean and hydrogen-preadsorbed Be(0001) surface

We systematically study the dissociation processes for hydrogen molecules on the Be(0001) surface. The minimum dissociation energy barrier is found to be 0.75 eV on the clean surface, and the dissociated hydrogen atoms are found to distribute universally on the Be surface. After hydrogen preadsorption, the dissociation energy barrier become 0.50 eV for molecular hydrogen on the Be surface. Our studies well describe the adsorption behaviors of hydrogen on the Be(0001) surface.     

Magnetic properties of AlN monolayer doped with group 1A or 2A nonmagnetic element: First-principles study

The electronic structure, magnetic properties, and mechanism of magnetization in two-dimensional(2D) aluminum nitride(AlN) monolayer doped with nonmagnetic elements of group 1A(Li, Na, K) or group 2A(Be, Mg, Ca) were systematically investigated using first-principles studies. Numerical results reveal that the total magnetic moments produced by group 1A and group 2A nonmagnetic doping are 2.0μB and 1.0μB per supercell, respectively. The local magnetic moments of the three N atoms around the doping atom are the primary moment contributors for all these doped AlN monolayers. The p orbital of the dopant atom contributes little to the total magnetic moment, but it influences adjacent atoms significantly, changing their density of states distribution, which results in hybridization among the p orbitals of the three closest N atoms, giving rise to magnetism. Moreover, the doped AlN monolayer, having half-metal characteristics,is a likely candidate for spintronic applications. When two group 1A or group 2A atoms are inserted, their moments are long-range ferromagnetically coupled. Remarkably, the energy of formation shows that, if the monolayer has been grown under N-rich conditions, substitution of a group 2A atom at an Al site is easier than substitution of a group 1A atom.