Observation of the dynamical change in a water monolayer adsorbed on a ZnO surface

A combined scanning tunneling microscopy and density-functional theory (DFT) study shows a rich structure of water monolayers adsorbed on ZnO(1010) at room temperature. Most of the water is in a lowest-energy configuration where every second molecule is dissociated. It coexists with an energetically almost degenerate configuration consisting of a fully molecular water monolayer. Parts of the layer continuously switch back and forth between these two states. DFT calculations reveal that water molecules repeatedly associate and dissociate in this sustained dynamical process.     

4He adsorbed on the outer surface of carbon nanotube bundles

The results of diffusion Monte Carlo calculations on the behavior of 4He adsorbed on the external surface of a bundle of carbon nanotubes are presented. The corrugation effects are found to be very important, making the outside part of the bundles a quite inhomogeneous substrate. No stable solid helium monolayer at high density was found. Instead, helium atoms are promoted to a second quasi-one-dimensional phase on top of the liquid first layer. On increasing the helium intake, a two layer structure is formed in which the helium directly in contact with the carbon surface solidifies.     

Experimental development of reflection-absorption spectroscopy: Infrared spectrum of carbon monoxide adsorbed on copper and copper oxide

The reflection-adsorption technique is used to obtain the infrared spectrum of a monolayer or less of carbon monoxide adsorbed on an evaporated copper film. The band is located at 2105 cm⁻¹ and is obtained with a signal-to-noise ratio in the range 5 to 15. In this technique, the infrared beam is multiply reflected between two closely-spaced parallel metal surfaces covered with the adsorbed layer. The CO band is used to investigate the dependence of the signal-to-noise ratio on the spacing of the metal surfaces. The existence of an optimum value of the spacing is demonstrated. The contribution to the absorption band of infrared rays with different angles of incidence is investigated and explained in terms of an optimum number of reflections and its variations with angle of incidence. After the copper surface is progressively exposed to oxygen, a slight shifting of the CO band to 2113 cm⁻¹ is observed. Further exposure gives rise to a new band of adsorbed CO at 2135 cm⁻¹, interpreted as CO adsorbed on copper oxide.     

Scanning tunneling microscopy and spectroscopy investigations of copper phthalocyanine adsorbed on Al2O3/Ni3Al(1 1 1)

Low temperature scanning tunneling microscopy (LT-STM) and scanning tunneling spectroscopy (STS) have been used to investigate adsorbed copper phthalocyanine (C₃₂H₁₆N₈Cu) molecules on an ordered ultrathin Al₂O₃ film on the Ni₃Al(1 1 1) surface as a function of coverage and annealing temperature. For sub-monolayer coverage and a deposition temperature of 140 K two different planar molecular adsorption configurations rotated by 30° with respect to each other were observed with submolecular resolution in the STM images. The template effect of the underlying oxide film on the CuPc orientation, however, is only weak and negligible at higher coverages. For θ_CuPc ≈ 1 ML, before completion of the first layer, the growth of a second layer was already observed. The measured spacing of 3.5 Å between first and second layer corresponds to the distance between the layers in the α-modification of crystalline CuPc. The molecules deposited at 140 K are thermally stable upon prolonged annealing to temperatures up to 250 K. By the use of STS the lowest unoccupied molecular orbital (LUMO) of the adsorbed copper phthalocyanine molecules has been identified at an energy of 1.2 eV above E_F. The lateral distribution of the electronic states of the CuPc has been analyzed and mapped by STS.     

Ar and Kr adsorption on Ag(111)

Precise structural and thermodynamic studies of Kr and of Ar adsorbed on Ag(111) are made using low energy electron diffraction. The phase diagram, lattice constants of the unconstrained monolayer and of the monolayer in equilibrium with the bilayer, latent heats of adsorption and isosteric heats are measured. The results are similar to those of an earlier study of Xe adsorbed on Ag(111). The results are compared to model calculations using effective lateral interactions which are similar to those for Xe/Ag(111). Comparison of the results for Xe, Kr, and Ar on Ag(111) is made using corresponding states scalings. A comparison is also made with properties of the non-registry phases of Xe, Kr, and Ar on basal plane graphite.     

Formation of the second layer of krypton on the cleavage face of calcium iodide; Further evidence of the importance of entropy in physisorption

From the analysis of a set of stepped adsorption isotherms of krypton on the cleavage face of calcium iodide, it is concluded that, above 70.5 K, a second adsorbed monolayer is formed, having an apparent molar energy (algebraic value) and entropy higher than those of the bulk phase of the adsorbate. The differences in energy and entropy are exceptionally high for a second layer, and consequently, when the temperature is lowered below 70.5 K, the pressure corresponding to the second step becomes higher than the sublimation pressure and the step disappears. This unusual observation of a second dense monolayer existing only because of its high entropy, again emphasizes the fundamental importance of entropy in physical adsorption. It is secondarily noted that the isotherms present evidence of interparticle condensation occurring at high relative pressures.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

On the 2D-3D transition in epitaxial thin film growth

The theory is based on the fact that the equilibrium concentration of single atoms adsorbed on the surface of a monolayer island placed on a foreign substrate such that the substrate-deposit interaction is weaker than the deposit-deposit interaction is higher than the equilibrium concentration of atoms adsorbed on the surface of the same island now placed on a substrate of the same material. This higher adatom concentration leads to 2D nucleation on top of the monolayer island. The difference of the above equilibrium adatom concentrations appears as a driving force for the process of transformation of the initial monolayer island into a 3D island by detachment of atoms from the first monolayer island edges and their subsequent attachment to the edges of the second layer nucleus. The kinetics of this process are studied in detail, the following two cases being considered. The first case consists of breaking up and agglomeration of an initially continuous film into 3D crystals upon heating. The second case consists of change of the growth mode from layer to island mode during the vapour deposition when the substrate temperature increases. Expressions for the critical temperatures for these two phenomena to occur are derived. It is shown that they depend strongly on the substrate orientation, the critical temperature being higher for the 〈111〉 orientation in comparison with the 〈110〉 orientation, if substrate and deposit with a fcc lattice are considered. The theoretical results are compared with experimental data for deposition of Au on Mo{110}, Cu on W{110} and W{100} and Fe on Cu{111}.     

有机分子隔离层对机械抛光金属银表面的罗丹明6G荧光增强效应的影响

采用物理吸附法,在机械抛光纯银表面引入对巯基苯胺(p-Amiothiophenol,PATP)分子充当隔离层,运用激光光谱学方法研究隔离层对位于银表面附近的罗丹明6G(Rh6G)分子的荧光增强效应影响。实验结果表明,未经PATP分子修饰的机械抛光金属衬底对Rh6G分子表现为猝灭效应,而经过PATP分子修饰后的银表面对Rh6G分子的荧光发射具有增强效应。根据局域表面等离子共振及辐射能量转移模型对实验观测所得结果进行了分析研究,结果表明,PATP有机分子隔离层的引入有效地减小了荧光分子与金属衬底之间的无辐射能量速率,提高了荧光辐射强度。     

Coverage dependence of neopentane trapping dynamics on Pt(111)

Adsorption probabilities for neopentane on Pt(111) were measured directly using supersonic molecular-beam techniques at coverages ranging from zero to monolayer saturation, incident translational energies between 18 and 110 kJ mol⁻¹ and incident angles between 0° and 60° at a surface temperature of 105 K. The adsorption probability was found to increase with coverage up to near monolayer saturation at all incident translational energies and incident angles. The coverage dependence of the adsorption probability predicted by a modified Kisliuk model with enhanced trapping into the second layer exhibits good quantitative agreement with the experimental values. The angular dependence of the adsorption probability decreases with increasing coverage, suggesting that the effective corrugation of the gas–surface interaction potential increases with the adsorbate coverage. The initial adsorption probability into the second layer onto the covered surface decreases from 0.95 to 0.75 with increasing energy over the energy range studied, and exhibits total energy scaling. A comparison with second-layer trapping data of simpler molecules onto covered Pt(111) indicates that the structural complexity of adsorbed neopentane molecules facilitates collisional energy transfer during adsorption.     

The effect of oxygen coverage on surface relaxation of Ni(110) measured by medium energy ion scattering

Changes have been observed in the upper layer spacing of a clean and an oxygen covered Ni(110) single crystal by employing medium energy ion scattering, combined with channeling and blocking. We find a contraction of 4% for the clean surface and a minor expansion of 1% for a surface with $\text{1}\text{3}$ monolayer of adsorbed oxygen.     

Neutron scattering study of the structure and dynamics of butane adsorbed on graphite2

Inelastic and elastic neutron scattering have been used to study the dynamics and structure of monolayer films of butane (CH₃(CH₂)₂CH₃) adsorbed on a graphitized carbon powder at 77 K. In addition to the intramolecular torsional modes found in the bulk solid, the inelastic spectra of the films contain new excitations associated with coupling of the molecular motion to the substrate. Model calculations are described which show the monolayer excitation spectrum to be sensitive to the orientation of the adsorbed butane molecule and the location and strength of the bonds to the substrate. For butane we infer that the molecule is adsorbed with the plane of the carbon skeleton parallel to the graphite layers. We have also used elastic neutron diffraction to investigate the possibility of long-range order in the butane films. Although we have not found Bragg peaks indicative of an ordered two-dimensional structure in a 1.5 layer film at 81 K, a large modulation of the graphite 002 Bragg reflection is observed. The experimental approach discussed here would seem to be applicable to the study of the dynamics, molecular orientation, and bonding of other hydrogenous adsorbates as a function of film thickness and temperature. Measurements are presently being extended to propane (CH₃CH₂CH₃) and ethane (CH₃CH₃) adsorbed on graphite.     

The structure of ammonia molecules on MgO(100) surfaces from monolayer to bulk condensation

The structure of ND₃ molecules adsorbed on MgO (100) surfaces has been studied by neutron diffraction within the 10–80 K temperature range and at 0.7, 1 and 2.3 monolayer coverage. The neutron spectra suggest that the monolayer presents a short range order with a hcp packing of ammonia molecules, a coherence length of 25 ± 2 Å and a nearest neighbour distance of 3.61 ± 0.04 Å The molecular spacing remains the same between 10 and 80K that we interpret as small higher order commensurate islands. Above one monolayer coverage, bulk crystallites form on top of the first monolayer.     

Pattern formation and localized structures in monoatomic layer deposition

We study the nonlinear robust behaviors of a model for the deposition of a monolayer of molecules on a surface which takes into account the interactions of the adsorbed molecules. The transport properties of the model lead to non Fickian diffusion. It is shown that we have generically Turing structures coexisting with uniform concentrations and consequently localized structures through the pinning mechanism. The characteristic lengths are in the nanometer region in agreement with recent experiments.     

Thermodynamics of xenon adsorption on Pd(s)[8(100) × (110)]: From steps to multilayers

The thermodynamic properties of the adsorption of xenon on the stepped Pd(s)[8(100)×(110)] surface have been studied over a wide range of pressure (5×10^?11 to 1×10^?4 Torr) and temperature (40–140 K). We have measured adsorption isobars using AES in order to evaluate the surface coverage. By choosing pressure and temperature we have studied under equilibrium conditions, the successive adsorption of xenon on the steps and on the terraces until the first layer is formed, the condensation of the second layer as well as the formation of xenon multilayers. For a small range of pressure and temperature, adsorption takes place only on the atomic steps. The LEED pattern shows that only every other site along the steps is occupied. The extrapolated initial heat of adsorption for steps is E_ad^S = 10.2 kcal/mol, decreasing monotonically by about 2 kcal/mol as the relative coverage of the step sites increases. The dipole moment of the Xe atoms adsorbed on steps is 1.12 D. During adsorption on the terraces the LEED observations suggest that the xenon adlayer is non-localized up to completion of the hexagonally close packed monolayer. The initial heat of adsorption on the terraces, E_ad^T is 8.2 kcal/mol and decreases continuously to a value of 6.9 kcal/mol for a complete monolayer due to lateral repulsive interactions between the adsorbed xenon atoms. The induced dipole moment of Xe on terraces is reduced to 0.49 D. The 5p_{$\text{1}\text{2}$} binding energy of Xe adsorbed on terrace sites is 0.3 eV smaller than that of Xe occuping step sites. The differential molar entropy of the adsorbed layer on the terraces as a function of coverage compares fairly well with the calculated value for an ideally mobile two-dimensional gas. No indication of the growth of two-dimensional xenon islands has been found under these conditions. The isosteric heat of adsorption for the second layer is E_ad^sec = 5.8 kcal/mol independently of the coverage. The condensation of the second layer is a first order two-dimensional gas ? two-dimensional solid phase transition in opposition to the continuous nature of the adsorption of the first layer (extending over a wide range of temperature for a given pressure). The induced dipole moment is further reduced for the Xe second layer to a value of 0.11 D. Finally, the condensation of multilayers proceeds with a latent heat of transformation of E_cond = 3.8 kcal/mol in excellent agreement with the known bulk value for the heat of sublimation of xenon. The line shape of the NVV low energy Auger transitions of xenon or the UPS binding energies of the Xe 5p_{$\text{3}\text{2}$,$\text{1}\text{2}$} spectra allow a clear distinction between first, second and higher layer Xe atoms. We have also established the temperature/pressure conditions for equilibrium between first, second and bulk xenon layers, i.e. a so-called “roughening point”.     

吸附氦(4He)薄膜准二维运动的有效势近似

对氦单层和氦二层体系的第二层低密度量子气体,依简化的准二维运动物理模型,求得了被吸附在石墨基底上的氦原子对之间的有效相互作用。由这种有效相互作用所求得的被吸附量子气体的第二维里系数及其二阶导数,比由理想二维物理模型出发所得结果更接近实验数据。 关键词：     

Decomposition pathways of C1C4 alcohols adsorbed on platinum (111)

The adsorption and decomposition of methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol has been studied on clean, and oxygen pre-covered Pt(111) surfaces. Temperature Programmed Reaction Spectroscopy (TPRS), Surface Potential Measurements (ΔV), UPS and XPS were used to characterise the adsorbed layer as a function of temperature. Each alcohol adsorbed into two states, a monolayer phase and a multilayer phase which were distinguishable by TPRS and Spectroscopy measurements. The monolayer alcohol adsorption heats increased sequentially from methanol to n-butanol (11.5–15 kcal mole^?1). On the clean surface, less than 10% of the adsorbed monolayer dissociated, with 90% of the alcohol desorbing intact. Two competing dissociative pathways were observed: complete dissociation to adsorbed CO, H and C, and with propan-1-ol and butan-1-ol, scission of the CC bond nearest the CO group to form adsorbed CO, H and ethylidyne and propylidyne species respectively. The latter reaction probability was constant at 30% for n-propanol and n-butanol. In all cases the final desorption products were the parent alcohol, CO and H₂ with carbon remaining on the surface for the higher alcohols. Atomic oxygen removed hydrogen from the alcohols as water but did not change the final reaction products.     

Leed study of Fe epitaxially grown at 190°C on Cu(100)

We report a LEED study of iron deposited on Cu(100) at 190°C. Very sharp LEED patterns were obtained for high iron coverages. We observed evidence of an ill defined Fe/Cu interface for one monolayer of iron deposited at 190°C. The stability of the iron overlayers was tested as a function of time for various coverages. For one monolayer the intensity versus energy curve for the (00) beam shows time dependence at 190°C. For four layers, no significant changes were observed in the LEED spectra over a period of one hour. We measured for five layers of iron a top layer expansion of 2.8% relative to the bulk. The interplanar spacing for bulk fcc Fe at 190°C remains equal to the room value. In these experiments the samples were deposited at 190°C and kept at this temperature during the LEED measurements.