Prominence of Terahertz Acoustic Surface Plasmon Excitation in Gas-Surface Interaction with Metals.

The current understanding of the dynamics of gas-surface interactions is that all of the energy lost in the collision is transferred to vibrations of the target. Electronic excitations were shown to play a marginal role except for cases in which the impinging particles have energies of several electronvolts. Here we show that this picture does not hold for metal surfaces supporting acoustic surface plasmons. Such loss, dressed with a vibronic structure, is shown to make up a prominent energy transfer route down to the terahertz region for Ne atoms scattering off Cu(111) and is expected to dominate for most metals. This mechanism determines, e.g., the drag force acting on telecommunication satellites, which are typically gold-plated to reduce overheating by sunshine. The electronic excitations can be unambiguously discerned from the vibrational ones under mild hyperthermal impact conditions.

Influence of growing conditions on the reactivity of Ni supported graphene towards CO.

Free standing graphene is chemically inert but, as recently demonstrated, CO chemisorption occurs at low crystal temperature on the single layer grown by ethene dehydrogenation on Ni(111). Such layer is inhomogeneous since different phases coexist, the relative abundance of which depends on the growth conditions. Here we show by X ray photoemission and high resolution electron energy loss spectroscopies that the attained CO coverage depends strongly on the relative weight of the different phases as well as on the concentration of carbon in the Ni subsurface region. Our data show that the chemical reactivity is hampered by the carbon content in the substrate. The correlation between the amount of adsorbed CO and the weight of the different graphene phases indicates that the top-fcc configuration is the most reactive.

CO chemisorption at vacancies of supported graphene films: a candidate for a sensor?

We investigate CO adsorption at single vacancies of graphene supported on Ni(111) and polycrystalline Cu. The borders of the vacancies are chemically inert but, on the reactive Ni(111) substrate, CO intercalation occurs. Adsorbed CO dissociates at 380 K, leading to carbide formation and mending of the vacancies, thus preventing their effectiveness in sensor applications.

Spontaneous Oxidation of Ni Nanoclusters on MgO Monolayers Induced by Segregation of Interfacial Oxygen.

We report the study of Ni nanoclusters deposited on MgO/Ag(100) ultrathin films (one monolayer) at T = 200 K. We show by STM analysis and DFT calculations that in the limit of low Ni coverage the formation of nanoclusters of four to six atoms occurs and that these aggregates are flat rather than 3D, as expected for Ni tetramers, pentamers, or hexamers. Both the shape of the clusters and the interatomic distance between neighboring Ni atoms are indicative that the nanoparticles do not consist of pure metal atoms but that a NiyOx structure has formed thanks to the availability of atomic oxygen accumulated at the MgO/Ag interface, with Ni clusters acting as oxygen pumps. Besides being of relevance in view of the use of metal nanoclusters in catalysis and other applications, this finding gives a further proof of the peculiar behavior of ultrathin oxide films.

Anisotropic dispersion and partial localization of acoustic surface plasmons on an atomically stepped surface: Au(788).

Understanding acoustic surface plasmons (ASPs) in the presence of nanosized gratings is necessary for the development of future devices that couple light with ASPs. We show here by experiment and theory that two ASPs exist on Au(788), a vicinal surface with an ordered array of monoatomic steps. The ASPs propagate across the steps as long as their wavelength exceeds the terrace width, thereafter becoming localized. Our investigation identifies, for the first time, ASPs coupled with intersubband transitions involving multiple surface-state subbands.

Spectroscopic evidence for neutral and anionic adsorption of (S)-glutamic acid on Ag(111).

We report here on a combined photoemission and vibrational spectroscopy investigation of (S)-glutamic acid adsorption on Ag(111). We show that, in the temperature range 250 K ≤ T ≤ 400 K, non-zwitterionic adsorption takes place and the anionic form prevails at nonvanishing coverage. Significant conformational changes of the self-assembled layer must occur above 300 K, corresponding to a substantial reduction of the sticking probability and a modification of the vibrational spectrum. The similarity of behavior with respect to glutamic acid adsorption on the previously investigated Ag(100) and Ag(110) surfaces is also discussed.

Correlated motion of electrons on the Au(111) surface: anomalous acoustic surface-plasmon dispersion and single-particle excitations.

The linear dispersion of the low-dimensional acoustic surface plasmon (ASP) opens perspectives in energy conversion, transport, and confinement far below optical frequencies. Although the ASP exists in a wide class of materials, ranging from metal surfaces and ultrathin films to graphene and topological insulators, its properties are still largely unexplored. Taking Au(111) as a model system, our combined experimental and theoretical study revealed an intriguing interplay between collective and single particle excitations, causing the ASP associated with the Shockley surface state to be embedded within the intraband transitions without losing its sharp character and linear dispersion.

Coupling scanning tunneling microscope and supersonic molecular beams: a unique tool for in situ investigation of the morphology of activated systems.

We report here on a new experimental apparatus combining a commercial low temperature scanning tunneling microscope with a supersonic molecular beam. This setup provides a unique tool for the in situ investigation of the topography of activated adsorption systems and opens thus new interesting perspectives. It has been tested towards the formation of the O/Ag(110) added rows reconstruction and of their hydroxylation, comparing data recorded upon O(2) exposure at thermal and hyperthermal energies.

Poisoning and non-poisoning oxygen on Cu(410).

We have investigated ethene and oxygen co-adsorption on Cu(410) by high resolution electron energy loss spectroscopy. We find that these two species compete for the adsorption sites and that pre-exposure to oxygen affects ethene adsorption more or less strongly depending on oxygen coverage and the kind of occupied sites. The c(2 × 2) O overlayer is inert with respect to ethene adsorption, while when some oxygen is removed by thermally induced subsurface incorporation, ethene chemisorption is restored. The latter species also adsorbs on the disordered oxygen phase formed when O(2) is dosed at low crystal temperature. Contrary to the bare surface case, most of the ethene ends up in a π-bonded configuration. Dehydrogenation occurs, too, albeit as a minority channel. The so-produced carbon reacts already at low temperature with adsorbed oxygen to yield carbon monoxide, which desorbs around 190 K.

Stoichiometry-dependent chemical activity of supported MgO(100) films.

Here, we show that the stoichiometry and, consequently, the chemical activity toward hydroxylation of MgO(100) films grown by reactive deposition on Ag(100) strongly depend on the O(2) partial pressure during film growth. Oxygen-deficient films undergo dramatic relative oxygen uptake either by exposure to a partial pressure of water vapor or by aging in vacuum for a sufficiently long time. Conversely, on stoichiometric monolayer MgO islands, photoemission analysis of the O 1s level and scanning tunneling microscopy images are consistent with the prediction that dissociative adsorption of water occurs only at the borders of the islands.

(S)-glutamic acid on Ag(100): self-assembly in the nonzwitterionic form.

The fundamental understanding of adsorption and self-organization of biological molecules at surfaces is of greatest importance for a huge variety of possible applications, ranging from molecular electronics to the study of biocompatible materials, hygiene, and biofouling. In spite of that, the characterization of the interactions of organic molecules of biological interest with surfaces is far from being complete. In the present paper we report on a combined microscopic (scanning tunneling microscopy (STM)) and spectroscopic (X-ray photoemission spectroscopy and high-resolution electron energy loss spectroscopy) study of glutamic acid (Glu) adsorption and self-assembly on Ag(100) at different temperature. STM allows one to determine the structures of the Glu layers, for which empirical models are proposed, while photoemission spectra exclude adsorption in the zwitterionic form, which is the most common especially for weakly interacting substrates.

Self-assembly of (S)-glutamic acid on Ag(100): a combined LT-STM and ab initio investigation.

Self-assembly of organic molecules at metal surfaces is of greatest importance in nanoscience; in fact, it opens new perspectives in the field of molecular electronics and in the study of biocompatible materials. Combining an experimental low-temperature scanning tunneling microscopy investigation with ab initio calculations, we succeeded to describe in detail (S)-glutamic acid adsorption on Ag(100) at T = 350 K. We find that (S)-glutamic acid organizes in a squared structure and, at variance with the majority of cases reported in literature, it adsorbs in the neutral form, 4.6 A above the surface plane. The interaction with the poorly reactive Ag substrate is only due to weak van der Waals forces, while H-bonds between carboxyl groups and the formation of a OCOH-OCOH-OCOH-OCOH cycle at the vertex of the squares are the main responsible for the self-assembly.

O(2) dissociation before the onset of added row nucleation on Ag(110): an atomistic scanning tunnelling microscopy view.

We present here a scanning tunnelling microscopy (STM) study on O(2) adsorption at Ag(110) at T = 175 K, i.e. in the temperature range between the onset of O(2) dissociation and the formation of the added row reconstruction. In agreement with previous studies at lower surface coverage, we observe several structures forming upon O(2) dissociation, including Ag-O complexes randomly distributed on the surface. We suggest that the presence of the latter structures, characterized by a large cross section for low energy electrons, can account for the marked decrease of the surface electron reflectivity and for the corresponding increase of the diffuse elastic intensity previously reported in a HREELS investigation of the same system.

Tuning the stoichiometry of surface oxide phases by step morphology: Ag(511) versus Ag(210).

We show by vibrational and photoemission spectroscopy and by ab initio calculations that in ultrahigh vacuum oxygen adsorption at stepped Ag surfaces causes the formation of surface oxide phases with different stoichiometry, depending on the morphology of the steps involved in the nucleation process. On Ag(511), characterized by close-packed steps and (100) terraces, subsurface O occupies tetrahedral interstitials and an Ag2O-like phase forms; on Ag(210), showing open step edges, subsurface oxygen ends up off center in octahedral sites and an AgO-like structure nucleates.

Monitoring super- and subsurface oxygen on Ag(210) by high energy resolution X-ray photoelectron spectroscopy: subsurface diffusion and segregation.

We report on a high energy resolution X-ray photoelectron spectroscopy plus supersonic molecular beam investigation of O/Ag(210). Two components are detected in the O1s spectra upon O2 adsorption, at binding energies EB=527.7 and 529.6 eV. The former peak persists up to 470 K, while the latter one decreases abruptly above 280 K. Comparison with a previous vibrational spectroscopy investigation on the same system (L. Vattuone, et al. Phys. Rev. Lett. 2003, 90, 228302) allows to assign both features to atomic oxygen. The low-energy peak is identified with adatoms, while the other is correlated to O atoms in subsurface sites. A minor contribution at the same binding energy, due to carbonates, is quantified by inspection of the C1s region and shows a different temperature behavior with respect to oxygen. Oxygen segregation into the subsurface region is observed when heating the crystal in the presence of supersurface oxygen.

Molecular ordering and adsorbate induced faceting in the Ag{110}-(S)-glutamic acid system.

The adsorption of the amino acid, (S)-glutamic acid, was investigated on Ag{110} as a function of coverage and adsorption temperature using the techniques of scanning tunneling microscopy, low energy electron diffraction, and reflection absorption infrared spectroscopy. In the monolayer, (S)-glutamic acid was found to adsorb predominantly in the anionic glutamate form. Several discrete ordered adlayer structures were observed depending on preparation conditions. In addition, (S)-glutamic acid was found to induce both one- and two-dimensional faceting of the Ag{110} surface. In some cases, evidence was found that the 2-D faceting involved the creation of a chiral facet distribution. A comparison is made of the Ag/(S)-glutamic acid system with analogous studies of amino acids on Cu.

Dynamics of propene adsorption on Ag001.

The interaction of propene with Ag(001) is investigated by high resolution electron energy loss spectroscopy and supersonic molecular beam methods under ultra high vacuum conditions. Propene adsorbs molecularly at 110 K and desorbs intact leaving a clean surface after annealing to 160 K. Two adsorption sites, characterized by slightly different vibrational modes, exist. The low frequency species is observed already at low coverage for molecules impinging at strongly hyperthermal energies while at lower translational energy it appears only at high coverage. The initial sticking probability S(0) decreases with increasing translational energy, as appropriate for nonactivated adsorption systems. The angle and energy dependence of S(0) indicate that scaling is intermediate between total and normal energy. From the coverage dependence of the sticking probability we infer that both a nonthermal intrinsic and a thermal extrinsic precursor exist.

Stereodynamic effects in the adsorption of propylene molecules on Ag(001).

We report on the experimental evidence of the role of rotational alignment of the gas-phase molecules in the interaction of propylene with Ag(001). Molecular alignment has been controlled by a velocity selection of the impinging molecules, flying in a supersonic seeded molecular beam. The experimental findings indicate that at low surface coverage the sticking probability is independent of molecular alignment, while when coverage exceeds few percent of a monolayer, molecules impinging rotating parallel to the surface (helicopter-like configuration) achieve a higher chance to be trapped than those which impinge rotating perpendicularly (cartwheels). The sudden appearance of a large stereodynamic effect suggests that the adsorption proceeds via a mobile precursor state and is tentatively correlated with a change in the configuration of the added propylene molecules, which adsorb tilted rather than flat at the surface.

Direct access to subsurface sites in gas-surface O2/Ag210 interactions using supersonic molecular beams.

We show with supersonic molecular beams and surface vibrational spectroscopy that, contrary to the case of Ag(100) and Ag(110), O2 undergoes total dissociation on Ag(210) at 105 K. Moreover, metastable subsurface sites can be accessed either directly or indirectly. For the direct channel, the final configuration of the oxygen atoms depends on the angle and the energy with which the gas-phase molecules collide with the surface, being largest for normal incidence on the (100) nanofacets. Access into the subsurface site is enabled only in the presence of preadsorbed oxygen adatoms.

Role of steps and of terrace width in gas-surface interaction: O2/Ag(410).

We demonstrate by vibrational spectroscopy that open steps are the active site for O2 dissociation on Ag(410), and that the barrier to adsorption at defects can be measured by energy and angle resolved investigation of the dynamics of the gas-surface interaction. We identify a molecular adsorption channel with considerably reduced activation barrier and a nonactivated dissociative pathway. The O2 sticking probability is increased at steps and strongly reduced at terraces with respect to Ag(100), implying that reactivity is influenced by terrace width.