HREELS Studies on Adsorption and Decomposition of ~(15)NO on Mo(100)-c(2×2)N Surface

MolybdenumnitridesascatalystsexhibituniquecataIyticactivitiesforawidevarietyofreactions,particularlyforthehydrodenitrogenationintherefineryprocessingofcrudesl.However,thefundamentalunderstandingconcerningthereactionmechanismsovermolybdenumnitrideisnotasweIlestablishedasthatontheMosurface.APplicationofpowerfulsurfacesciencespectroscopiesonwell-characterizednitrideoverlayersshouldprovideimPortantinsightsintothesurfacestrllctureandreactivityofsuchimportantcatalyticmaterials.Inthepresentwork,ahi…     

The isomeric effect on the adjacent Si dimer didechlorination of trans and iso-dichloroethylene on Si(100)-2×1

The dechlorination processes of isomers trans and iso-dichloroethylene (iso-DCE) on Si(100)-2×1 were investigated from first principles, to ascertain the isomeric effect on the adjacent Si dimer di-dechlorination of DCE on Si(100)-2×1. By comparing the feasible adspecies and their reaction barriers between trans and cis-DCE on Si(100)-2×1, we found that the isomeric effect of trans-DCE is negligible, which explained the similar C 1s peak locations in the X-ray photoelectron spectroscopy (XPS) experiment. In contrast, iso-DCE undergoes a more complicated reaction process, although the adjacent Si dimer di-dechlorination is still the dominant mechanism. Among the initial competitive reactions involving intra-, inter-cycloaddition and single C-Cl cleavage, the barrierless intra-cycloaddition is the most favorable reaction and precludes the single dechlorination that yields the mono-σ structure. Subsequent di-dechlorination undergoes a three-step reaction to yield the final product intra-dimer tetra-σ. In addition, the ionization energies of C 1s and Cl 2s electrons were calculated for the tentative assignment of the peaks observed in XPS.     

W(100)c(2×2)表面的STM图像

用基于第一性原理的密度泛函理论研究了W(100)c(2×2)再构表面的表面弛豫以及扫描隧道显微镜(STM)图像和衬底偏压的关系.计算所得到的表面原子沿[110]方向的畸变位移δ为0.027nm,畸变能△E为80.6meV·atom-1,表面原子的弛豫分别为-7.6%(△d12/d0)和 0.8%(△d23/d0),功函数Φ为4.55eV.STM图像模拟表明,由于表面原子沿[110]方向的位移,会导致出现平行于[110]方向的亮暗带状条纹.STM图像中突起所对应的并不是表面或次表面的钨原子,而是zig-zag型W原子链中线位置;而STM暗区对应于原子位置畸变形成的相邻zig-zag型W原子链中间区域.当衬底负偏压时,STM针尖典型起伏高度大约在0.008-0.013nm之间;而当衬底正偏压时,针尖起伏高度在0.019-0.024nm之间变化.     

DFT Investigations About Pyrazine Molecules on Si(100)-2×1 Surface

It is important to understand the interface of aromatic molecules on semiconductor surfaces because of the rich functionality of such molecules on semiconductor surfaces.The chemisorption of pyrazine molecules on the Si(100)-2×1 surface has been investigated using the B3LYP density functional theory with Si9H12 one-dimer and Si15H16 two-dimer cluster models.The calculated results predict that N-dative bonded-state,C2-C5 [4 2] and the tight-bridge1,2,5,6 products may coexist on the Si(100)-2×1 surface.     

Adsorption and Reaction of CO on Mo(100)-c(2×2)-N Surface Studied by HREELS

Molybdenum nitrides have attracted significant attention recently due to their uniquephysical and chemical properties. Many studies have shown that Mo,N is an activecatalyst for CO hydrogenation. The fundamental understanding concerning the reactionmechanisms over Mo=N. however, is not well established. The powerful surface sciencetechniques may provide an insight into the surface structure and properties of such animportant catalytic material. In previous paper', we described the results o…     

Density functional theory simulations of amorphous high-κ oxides on a compound semiconductor alloy: a-Al2O3/InGaAs(100)-(4×2), a-HfO2/InGaAs(100)-(4×2), and a-ZrO2/InGaAs(100)-(4×2)

The structural properties of a-Al(2)O(3)∕In(0.5)Ga(0.5)As, a-HfO(2)∕In(0.5)Ga(0.5)As, and a-ZrO(2)∕In(0.5)Ga(0.5)As interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic amorphous a-Al(2)O(3), a-HfO(2), and a-ZrO(2) samples were generated using a hybrid classical-DFT MD "melt-and-quench" approach and tested against the experimental properties. For each stack type, two systems with different initial oxide cuts at the interfaces were investigated. All stacks were free of midgap states, but some had band-edge states which decreased the bandgaps by 0%-40%. The band-edge states were mainly produced by deformation, intermixing, and bond-breaking, thereby creating improperly bonded semiconductor atoms. The interfaces were dominated by metal-As and O-In∕Ga bonds which passivated the clean surface dangling bonds. The valence band-edge states were mainly localized at improperly bonded As atoms, while conduction band-edge states were mainly localized at improperly bonded In and Ga atoms. The DFT-MD simulations show that electronically passive interfaces can be formed between high-κ oxides dielectrics and InGaAs if the processing does not induce defects because on a short time scale the interface spontaneously forms electrically passive bonds as opposed to bonds with midgap states.     

Dynamics of H2 dissociation on the 1/2 ML c(2 × 2)-Ti/Al(100) surface

The dissociation of H(2) on Ti-covered Al surfaces is relevant to the rehydrogenation and dehydrogenation of the NaAlH(4) hydrogen storage material. The energetically most stable structure for a 1/2 monolayer of Ti deposited on the Al(100) surface has the Ti atoms in the second layer with a c(2 × 2) structure, as has been confirmed by both low-energy electron diffraction and low-energy ion scattering experiments and density functional theory studies. In this work, we investigate the dynamics of H(2) dissociation on a slab model of this Ti/Al(100) surface. Two six-dimensional potential energy surfaces (PESs) have been built for this H(2) + Ti/Al(100) system, based on the density functional theory PW91 and RPBE exchange-correlation functionals. In the PW91 (RPBE) PES, the lowest H(2) dissociation barrier is found to be 0.65 (0.84) eV, with the minimum energy path occurring for H(2) dissociating above the bridge to top sites. Using both PESs, H(2) dissociation probabilities are calculated using the classical trajectory (CT), the quasi-classical trajectory (QCT), and the time-dependent wave-packet methods. We find that the QCT H(2) dissociation probabilities are in good agreement with the quantum dynamics results in the collision energy range studied up to 1.0 eV. We have also performed molecular beam simulations and present predictions for molecular beam experiments. Our molecular beam simulations show that H(2) dissociation on the 1/2 ML Ti/Al(100) surface is an activated process, and the reaction probability is found to be 6.9% for the PW91 functional and 1.8% for the RPBE at a nozzle temperature of 1700 K. Finally, we have also calculated H(2) dissociation rate constants by applying transition state theory and the QCT method, which could be relevant to modeling Ti-catalyzed rehydrogenation and dehydrogenation of NaAlH(4).     

Stereo-isomerism controls surface reactivity: 1-chloropentane-pairs on Si(100)-2×1

Chloropentane forms asymmetric ('A') and symmetric ('S') pairs on Si(100)-2×1, differing in the direction of curvature of one pentane tail. Surprisingly this renders the rate of thermal reaction of 'A' fifteen times greater than 'S' in chlorinating room-temperature silicon. Correspondingly, for electron-induced reaction the energy threshold for A is 1 eV less than for S.     

Atomic imaging of atomic layer deposition oxide nucleation with trimethylaluminum on As-rich InGaAs(001) 2 × 4 vs Ga/In-rich InGaAs(001) 4 × 2

Formation of a contaminant free, flat, electrically passive interface to a gate oxide such as a-Al(2)O(3) is the critical step in fabricating III-V metal oxide semiconductor field effect transistors; while the bulk oxide is amorphous, the interface may need to be ordered to prevent electrical defect formation. A two temperature in situ cleaning process is shown to produce a clean, flat group III or group V rich InGaAs surface. The dependence of initial surface reconstruction and dosing temperature of the seeding of aluminum with trimethylaluminum dosing is observed to produce an ordered unpinned passivation layer on InGaAs(001)-(4 × 2) surface at sample temperatures below 190 °C. Conversely, the InGaAs(001)-(2 × 4) surface is shown to generate an unpinned passivation layer with a seeding temperature up to 280 °C. For both reconstructions, the chemical drive force is consistent with formation of As-Al-As bonds. The optimal seed layer protects the surface from background contamination.     

Six-dimensional quasiclassical and quantum dynamics of H2 dissociation on the c(2 × 2)-Ti/Al(100) surface

Based on a slab model of H(2) dissociation on a c(2 × 2) structure with Ti atoms in the first and third layers of Al(100), a six-dimensional (6D) potential energy surface (PES) has been built. In this PES, a molecular adsorption well with a depth of 0.45 eV is present in front of a barrier of height 0.13 eV. Using this PES, H(2) dissociation probabilities are calculated by the classical trajectory (CT), the quasiclassical trajectory (QCT), and the time-dependent wave-packet (TDWP) method. The QCT study shows that trajectories can be trapped by the molecular adsorption well. Higher incident energy can lead to direct H(2) dissociation. Vibrational pre-excitation is the most efficient way to promote direct dissociation without trapping. We find that both rotational and vibrational excitation have efficacies close to 1.0 in the entire range of incident energies investigated, which supports the randomization in the initial conditions making the reaction rate solely dependent on the total (internal and translational) energy. The H(2) dissociation probabilities from quantum dynamics are in reasonable agreement with the QCT results in the energy range 50-200 meV, except for some fluctuations. However, the TDWP results considerably exceed the QCT results in the energy range 200-850 meV. The CT reaction probabilities are too low compared with the quantum dynamical results.     

Theoretical Calculations on Amphoteric Adsorptions of the Hydrogenated C(100)-2×1 Surface

In this work we study the adsorptions of some small molecules or group on the hydrogenated C(100)-2×1 surface using density functional theory method. The calculated results show that the ionization potential (IP) of the hydrogenated C(100)-2×1 surfaces after adsorption has amphoteric characteristics. From the weak basic NH3 molecule with small IP and negative electron affinity (EA), through the neutral H2O molecule, to the weak acid HF molecule and the OH group with large EA and IP, the IP values of the adsorbed diamond surfaces vary from decrease, through invariability, to slight increase for HF and obvious increase for OH. In all adsorption species, only the OH group makes the hydrogenated C(100)-2×1 surface change to the metal from the semiconductor with a wide-band gap, while the others only introduce impurity states into the electronic structures of the hydrogenated C(100)-2×1 surfaces.     

Dynamics of scattering and dissociative adsorption on a surface alloy: H2/W(100)-c(2 × 2)Cu

H(2) scattering and dissociative adsorption on the W(100)-c(2 × 2)Cu surface alloy is studied based on DFT calculations. A strongly site dependent reactivity is observed in line with results obtained for the density of states projected onto the W and Cu atoms of the topmost layer. H(2) dissociation on a defect free terrace of W(100)-c(2 × 2)Cu is found to be a non-activated process like on W(100), despite the reduction of the number of energetically accessible dissociation pathways at low impact energies due to the presence of Cu atoms. A prominence of dynamic trapping and a reduction of the efficacy of trapping to promote dissociation is also verified, leading to a decrease of the initial sticking probability as a function of the molecular impact energy, in qualitative agreement with experimental findings. The heterogeneous reactivity is also evidenced by two different kinds of reflection events at low energies. Its combination gives rise to a broad specular peak superimposed on a cosine-like angular distribution of scattered molecules which is in good agreement with available experimental data.     

The selective recognition of mismatched d(GCGAGC)_2 by the cobalt(III) complex

Base mismatches arise naturally in the life cycleof a cell as a result of either polymerase error or DNAdamage. Under most circumstances the cell correctsthese mispairings using a complex repair system toprevent mutations in the genetic code. Experimental…     

The Synthesis of Poly(ethylene oxide)-Block-Polybutylacrylate

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Ru9Zn7Sb8: a structure with a 2 × 2 × 2 supercell of the half-Heusler phase

The title compound Ru(9)Zn(7)Sb(8) was synthesized via a high-temperature reaction from the elements in a stoichiometric ratio, and its structure was solved by a single-crystal X-ray diffraction method. The structure [cubic, space group Fm3m, Pearson symbol cF96, a = 11.9062(14) ? (293 K), and Z = 4] adopts a unique 2a(hh) × 2a(hh) × 2a(hh) supercell of a normal half-Heusler phase and shows abnormal features of atomic coordination against the Pauling rule. The formation of this superstructure was discussed in light of the valence electron concentration per unit cell. It is a metallic conductor [ρ(300 K) = 16 μΩ·m], and differential scanning calorimetry revealed that Ru(9)Zn(7)Sb(8) undergoes a transformation at 1356(1) K and melts, by all indications, congruently at 1386 K. At room temperature, its thermal conductivity is about 3 W/m·K, which is only one-quarter of that of most normal half-Heusler phases. Ru(9)Zn(7)Sb(8) as well as its analogues of iron-, cobalt-, rhodium-, and iridium-containing compounds are expected to serve as a new structure type for exploring new thermoelectric materials.     

Multiple pathways of dissociative attachment: CH3Br on Si(100)-2×1

We describe the dissociative attachment (DA) of methyl bromide to form chemisorbed CH(3) and Br on a Si(100)-2×1 surface at 270 K. The patterns of DA were studied experimentally by ultra-high vacuum scanning tunneling microscopy (STM) and interpreted by ab initio theory. The parent molecules were found to dissociate thermally by breaking the C-Br bond, attaching the resulting fragments CH(3) and Br at adjacent Si-atom sites. The observed DA resulted in three distinct attachment geometries: inter-row (IR, 88%), inter-dimer (ID, 11%), and on-dimer (OD, 1%). Ab initio computation agreed in predicting these three DA reaction pathways, with yields decreasing down the series, in accord with experiment. The three computed physisorption geometries, each of which correlated with a preferred outcome, IR, ID, or OD, exhibited similar heats of adsorption, the choice of pathway being governed by the energy barriers to DA chemisorption predicted to increase along the series: E(IR) = 0.48 eV, E(ID) = 0.57 eV, and E(OD) = 0.63 eV.     

Selective assembly of cyclodextrins on poly(ethylene oxide)–poly(propylene oxide) block copolymers

This paper presents a computational study on the formation of a molecular necklace formed by specific threading of cyclodextrins (CDs) on block copolymers. Structural as well as energetic principles for the selective complexation of - and -cyclodextrin with poly(ethylene oxide)–poly(propylene oxide) block copolymers (PEO–PPO) are elucidated considering a diblock copolymer of equimolecular composition (PEO)4–(PPO)4 as guest. A non-statistical distribution of CDs, i.e. -CDs primarily located on the PEO chain and -CDs on PPO blocks of the polymer, is based on a variety of structural features and energetic preferences considering both potential as well as solvation energies. This selectivity becomes already obvious considering 1:1 complexes between PEO and PPO monomers and the two CDs, but is increasingly evident when calculating higher order ensembles. Besides the host–guest interaction, docking between CDs themselves is an important, also non-statistical, prerequisite for the self-assembly of highly ordered tubes. The formation of intermolecular hydrogen bonds between adjacent CDs in a tubular aggregate gives an important contribution to the overall stability of the molecular necklace. The net effect, based on the preferential interaction between host and guest as well as between the host molecules themselves, results in the formation of a stable, highly ordered macromolecular, multicomponent aggregate.     

H atom adsorption and diffusion on Si(110)-(1×1) and (2×1) surfaces

We present a periodic density-functional study of hydrogen adsorption and diffusion on the Si(110)-(1×1) and (2×1) surfaces, and identify a local reconstruction that stabilizes the clean Si(110)-(1×1) by 0.51 eV. Hydrogen saturates the dangling bonds of surface Si atoms on both reconstructions and the different structures can be identified from their simulated scanning tunneling microscopy/current image tunneling spectroscopy (STM/CITS) images. Hydrogen diffusion on both reconstructions will proceed preferentially along zigzag rows, in between two adjacent rows. The mobility of the hydrogen atom is higher on the (2×1) reconstruction. Diffusion of a hydrogen vacancy on a monohydride Si(110) surface will proceed along one zigzag row and is slightly more difficult (0.2 eV and 0.6 eV on (1×1) and (2×1), respectively) than hydrogen atom diffusion on the clean surface.     

Palladium acetate complexes with morpholine and 4-methylmorpholine. The structure of Pd(C4H9ON)2(OAc)2 · 2H2O

Methods for the synthesis of new palladium(II) acetate complexes [L₂Pd(OCOCH₃)₂], where L is N-coordinated morpholine (C₄H₉ON) or 4-methylmorpholine (C₅H₁₁ON), have been developed. The structure of the complex (C₄H₉ON)₂Pd(OAc)₂ · 2H₂O (1) has been established by X-ray diffraction. The crystals of 1 are monoclinic (C₁₂H₂₆O₈N₂Pd, M = 434.76), space group P2(1)/c, a = 9.129(3) Å, b = 16.227(5) Å, c = 6.159(2) Å, V = 878.5(5) ų, Z = 2. The palladium atom has a square-planar environment with the trans arrangement of ligands. The complex (C₅H₁₁ON)₂Pd(OAc)₂ (2) has a similar structure, according to spectroscopic data.