Stranski-Krastanov growth of para-sexiphenyl on Cu(110)-(2×1)O revealed by optical spectroscopy

We have studied the growth of para-sexiphenyl (p-6P) on the Cu(110)-(2×1)O surface using reflectance difference spectroscopy (RDS) in combination with scanning tunneling microscopy (STM). The evolution of the optical anisotropy reveals that the growth of p-6P on the Cu(110)-(2×1)O surface at room temperature follows the Stranski-Krastanov growth mode with a two monolayer thick wetting layer. During all stages of growth, the p-6P molecules are well orientated with their long molecular axis aligned parallel to the Cu-O rows along the [001] direction of the Cu(110) substrate. The high packing density of the p-6P molecules in the first and second monolayer evidenced by RDS and STM is believed to be responsible for the switch from layer-by-layer to three-dimensional island growth.     

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.     

Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 × 1 surface

The water splitting reaction based on the promising TiO(2) photocatalyst is one of the fundamental processes that bears significant implication in hydrogen energy technology and has been extensively studied. However, a long-standing puzzling question in understanding the reaction sequence of the water splitting is whether the initial reaction step is a photocatalytic process and how it happens. Here, using the low temperature scanning tunneling microscopy (STM) performed at 80 K, we observed the dissociation of individually adsorbed water molecules at the 5-fold coordinated Ti (Ti(5c)) sites of the reduced TiO(2) (110)-1 × 1 surface under the irradiation of UV lights with the wavelength shorter than 400 nm, or to say its energy larger than the band gap of 3.1 eV for the rutile TiO(2). This finding thus clearly suggests the involvement of a photocatalytic dissociation process that produces two kinds of hydroxyl species. One is always present at the adjacent bridging oxygen sites, that is, OH(br), and the other either occurs as OH(t) at Ti(5c) sites away from the original ones or even desorbs from the surface. In comparison, the tip-induced dissociation of the water can only produce OH(t) or oxygen adatoms exactly at the original Ti(5c) sites, without the trace of OH(br). Such a difference clearly indicates that the photocatalytic dissociation of the water undergoes a process that differs significantly from the attachment of electrons injected by the tip. Our results imply that the initial step of the water dissociation under the UV light irradiation may not be reduced by the electrons, but most likely oxidized by the holes generated by the photons.     

Assessing Density Functionals for Describing Methane Dissociative Chemisorption on Pt(110)-(2×1) Surface

In this work, we explore the suitability of several density functionals with the generalized gradient approximation (GGA) and beyond for describing the dissociative chemisorption of methane on the reconstructed Pt(110)-(2\begin{document}$ \times $\end{document}1) surface. The bulk and surface structures of the metal, methane adsorption energy, and dissociation barrier are used to assess the functionals. A van der Waals corrected GGA functional (optPBE-vdW) and a meta-GGA functional with van der Waals correction (MS PBEl-rVV10) are selected for ab initio molecular dynamics calculations of the sticking probability. Our results suggest that the use of these two functionals may lead to a better agreement with existing experimental results, thus serving as a good starting point for future development of reliable machine-learned potential energy surfaces for the dissociation of methane on the Pt(110)-(2\begin{document}$ \times $\end{document}1) surface.     

Studies of surface processes of electrocatalytic reduction of CO_2 on Pt(210), Pt(310) and Pt(510)

Surface processes of CO2 reduction on Pt(210), Pt(310), and Pt(510) electrodes were studied by cyclic voltammetry. Different surface structures of these platinum single crystal electrodes were obtained by various treatment conditions. The experimental results illustrated that the electrocatalytic activity of Pt single crystal electrodes towards CO2 reduction is decreased in an order of Pt(210)>Pt(310)>Pt(510), i.e., with the decrease of (110) step density on well-defined surfaces. When the surfaces were reconstructed due to oxygen adsorption, the catalytic activity of all the three electrodes has been enhanced to a cer- tain extent. Although the activity order remains unchanged, the electrocatalytic activity has been en- hanced more significantly as the density of (110) step sites is more intensive on the Pt single crystal surface. It has revealed that the more open the surface structure is, the more active the Pt single crystal electrode will be, and the easier for the electrode to be transformed into a surface structure that exhib- its higher activity under external inductions. However, the relatively ordered surfaces of Pt single crystal electrode are comparatively stable under the same external inductions. The present study has gained knowledge on the interaction between CO2 and Pt single crystal electrode surfaces at a micro- scopic level, and thrown new insight into understanding the surface processes of electrocatalytic re- duction of CO2.     

High resolution Fourier transform spectroscopy of the PbO molecule from investigation of the O2(1Δg)—Pb reaction

From the reaction of Pb with metastable oxygen O₂(¹Δ_g) in a Broida type oven we have analysed at high resolution some vibrational levels of the X0⁺, a1, A0⁺ and B1 states of the ²⁰⁸PbO molecule. The rotational parameters determined allowed us to recalculate the position of the various isotope lines to within 0.01 cm⁻¹. We have found a negative value of ω_eχ_e (−0.123 (25) cm⁻¹) in A0⁺, contrary to previous observations. The Ω type doubling in a1 varies from +1.8 × 10⁻⁴ cm⁻¹ (υ′ = 2) to +2.3 × 10⁻⁴ cm⁻¹ (υ′ = 9) and in B1 from −1.17 × 10⁻⁴ cm⁻¹ (υ′ = 0) to −0.97 × 10⁻⁴ cm⁻¹ (υ′ = 2).     

NO Adsorption on Ag/Pt(110)-(1×2) Bimetallic Surfaces: Unexpected Formation of Nitrite/nitrate Surface Species

NO adsorption on Ag/Pt(110)-(1×2) bimetallic surfaces at room temperature was inves-tigated by means of Auger electron spectroscopy, X-ray photoelectron spectroscopy and thermal desorption spectroscopy. An unexpected formation of nitrite/nitrate surface species on Ag/Pt(110)-(1×2) bimetallic surfaces is observed, then decompose at elevated tempera-tures to form N₂. However, such nitrite/nitrate surface species do not form on clean Pt(110) and Ag-Pt alloy surfaces upon NO exposure at room temperature. The formation of ni-trite/nitrate surface species on Ag/Pt(110)-(1×2) bimetallic surfaces is attributed to highreactivity of highly coordination-unsaturated Ag clusters and the synergetic effect between Ag clusters and Pt substrate.     

Theoretical study of Aun clusters (n = 1–5) deposited on a rutile TiO2 (110) slab,concerning structure and stability

The initial nucleation of gold clusters Au_n (n = 1–5) on TiO₂ rutile (110) reduced surface is studied using density functional theory and a full-potential augmented-plane-wave method implemented in the WIEN2k code. The first two gold atoms remained tied to the surface with a bond length similar to those belonging to other well-known related materials, while the other gold atoms do not spread over the surface; they preferred to form a new layer. The occurrence of relativistic effects produced a preferential triangle geometry for Au₃ and a combination of triangular units for Au₄ and Au₅. The Au–Au average distance increased from n = 2 to n = 5, indicating an expansion with a tendency to the bond distance found in the bulk. We are reporting an early 2D→3D transition of small folding, from Au₃→Au₄, followed by an Au₄→Au₅ transition of evident 3D character.     

High resolution spectroscopy of the 13Σ g + (b) ← 13Σ u + (x) transition of Na2

Rotational-vibrational transitions of the triplet system 1³Σ _g ⁺ ← 1³Σ _u ⁺ of the Na₂ molecule have been investigated around $\bar v = 13970 cm^{ - 1} $ by Doppler-free polarization spectroscopy in a heat pipe and by resonant two-step photoionization in a collimated cold argon beam, seeded with sodium vapor. The fine- and hyperfine structure of the transitions is partly resolved. The analysis of the measured spectra and a theoretical discussion of the expected multiplet structure yields the rotational constantsB′ _v (v′=17)=0.0866(4) cm^?1 for the upper andB″ _v (v″=0)=0.0533(4) cm^?1 for the lower state. The difference Δb=b(³Σ _u )?b(³Σ _g ) of the hyperfine coupling constantsb turns out to be Δb=80 MHz.     

Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys

Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).     

High resolution spectral analysis of oxygen. II. Rotational spectra of a(1)Δ(g) O2 isotopologues

As part of a comprehensive review on molecular oxygen spectroscopy, we have measured rotational spectra of isotopic forms of molecular oxygen in its a(1)Δ(g) electronic state with high-resolution terahertz spectroscopy. The data are recorded in close proximity to predicted positions. Due to the high resolution and good signal-to-noise ratio, the fundamental hyperfine parameters eQq and C(I) are determinable for (17)O-substituted species for the first time. A refined nuclear spin orbit coupling constant, a = -211.9328(283) MHz, was determined, and is roughly two orders of magnitude more precise than values determined from near infrared spectroscopy or electron spin resonance studies. Vibrationally excited oxygen in the a(1)Δ(g) electronic state was also observable with small signal levels for many of the rotational transitions.     

Formation of sulfhydryl (SH) species on the clean and (2 × 2)-S covered Pt(111) surfaces by H2S decomposition

H₂S decomposition on the clean and (2 × 2)-S covered Pt(111) surfaces has been characterized using high-resolution electron energy loss (HREELS) and temperature-programmed desorption (TPD) spectroscopies. On the Pt(111)-(2 × 2)-S surface, a mixture of molecular H₂S and sulfhydryl (SH) species forms following H₂S adsorption at 110 K. The molecular H₂S desorbs at 140 K leaving a (2 × 2)-S overlayer saturated with SH; the SH is stable up to 190 K. On the clean Pt(111) surface, a mixture of atomic sulfur, SH and chemisorbed molecular H₂S is formed following H₂S adsorption at 110 K. On the clean surface, adsorbed SH decomposes near 150 K. We report here the first definitive observation of an adsorbed sulfhydryl species on a metal surface.     

Nature of the binding of a c(2×2)-CO overlayer on Ag(001) and surface mediated intermolecular coupling

We present a first-principles study of the nature of the binding of a c(2×2)-CO overlayer on Ag(001) and of the origin of CO-CO interactions upon adsorption. Electronic structural changes induced by molecular adsorption provide an interpretation for earlier X-ray photoemission valence band spectra of CO/Ag(001). Our results establish that CO chemisorbs on clean Ag(001) and follows the Blyholder model of donation and back-donation between CO and metal orbitals. We analyze the origin of the dispersion of the C-O stretch mode and attest that it is caused by the metal-CO coupling. Specifically, the coupling of CO to Ag, although the weakest of those between it and transition and other noble metals, greatly enhances the intermolecular force constants. We also find that the response of the charge density around CO is much stronger and of longer range when the molecule stretches than when it rigidly vibrates against the surface. This difference explains why the C-O stretch mode disperses while the Ag-CO stretch mode does not.     

STM and voltammetric studies on the structure of a 4-pyridinethiolate monolayer chemisorbed on Au(100)-(1×1) surface

The structure for a 4-pyridinethiolate monolayer chemisorbed on the Au(100)-(1×1) single crystal surface was characterized by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). In situ STM observation showed a well-ordered p(√2 R 45°×5 R 53.1°) structure (abbreviated as √2×5) for the surface modified with either 4-pyridinethiol (4-PySH) or bis(4-pyridyl)disulfide (4,4′-PySSPy) in a 0.05 M HClO₄ solution. On the Au(100)-(1×1) surface, 4-PySH molecules formed a dimer structure with the S–S bond length of about 2.4 nm. The observed dimer structure is similar to that previously reported on the Au(111) surface, and the orientation of the pyridine ring is mostly perpendicular to the surface normal. However, the adsorbed molecules were more densely packed (√3/√2 times) on the Au(100) surface than on the Au(111) surface. The surface excess was estimated to be 5.8 (±0.2)×10⁻¹⁰ mol cm⁻² based on the voltammetric charge for the reductive desorption. This value is in good agreement with that (5.7×10⁻¹⁰ mol cm⁻²) calculated from the parallelogrammic (√2×5) unit cell. The Au(100)-(1×1) surface modified with 4-PySH gave a well-defined electrochemical response of cytochrome c.     

Enzymatic resolution of (±)-cis- and (±)-trans-1-aminoindan-2-ol and (±)-cis- and (±)-trans-2-aminoindan-1-ol

Pseudomonas cepacia lipase (PSL) efficiently catalyses the kinetic resolution of (±)-cis- and (±)-trans-1-aminoindan-2-ol through the O-acylation reaction of the corresponding N-benzyloxycarbonyl derivative using vinyl acetate as the acyl donor. In a similar way, cis-N-Cbz-2-aminoindan-1-ol is resolved when isopropenyl acetate is used as the acylating agent. The enantioselectivity of the reaction was lower for (±)-trans-N-Cbz-2-aminoindan-1-ol due to the different steric requirements for the two conformers of this substrate.     

Theoretical Studies of H＿2O Adsorption on Pure and Pt Loading TiO＿2（Rutile）（110） Surfaces

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Comparison of neutron capture spectra taken by a constellation Xe-110 detector and a 1″×1″ NaI(Tl) crystal

Constellation Technology Corporation has developed a spectroscopic nuclear detector called the Xe-110 that is well suited for downhole use in oil and gas well logging. The advantages possessed by this detector over traditional technologies such as NaI(Tl) scintillators are summarized. We discuss an analysis of gamma-ray spectra taken by the Xe-110, which suggests that the superior energy resolution and low background level of this detector enables identification of important features in neutron activation spectra of hydrocarbons that might not be identifiable using an NaI(Tl) crystal.     

A DFT study on the interaction of Co with an anatase TiO2 (001)-(1×4) surface

The substitution/adsorption structures of Co on an anatase TiO2 (001)-(1×4) surface are investigated using the DFT/local density approximation (LDA) method.Theoretical calculation shows that the Co ion prefers to be adsorbed on the surface of anatase TiO2.The density of states (DOS) analysis finds that the Co 3d is located mainly in the energy gap region.The Co 3d partial density of states (PDOS) indicates that there is a substantial degree of hybridization between O 2s and Co 3d in valence band (VB) regions in the substitution models.The conclusion is that the mode of substitution is more active when the catalyst is a higher-energy surface.     

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.