Plinio Maroni

Surface reactivity of highly vibrationally excited molecules prepared by pulsed laser excitation: CH4 (2ν3) on Ni(100)

We report state resolved sticking coefficients for highly vibrationally excited CH4 on Ni(100) at well-defined kinetic energies in the range of 12-72 kJ/mol. Incident methane molecules are prepared by pulsed laser radiation in single rovibrational levels of the first overtone of the antisymmetric stretch (2nu(3)) at 6004.69 cm(-1) and collided at normal incidence with a clean Ni(100) single crystal. We find that the vibrational excitation enhances the reaction probability by a factor 100 at an incident translational energy of 72 kJ/mol, but this enhancement increases to more than 4 orders of magnitude at low kinetic energy. Despite this large increase in the sticking coefficient, vibrational energy in 2nu(3) appears to be about 80% as effective as an equivalent amount of translational energy in promoting the chemisorption reaction

Ordered and oriented supramolecular n/p-heterojunction surface architectures: completion of the primary color collection

In this study, we describe synthesis, characterization, and zipper assembly of yellow p-oligophenyl naphthalenediimide (POP-NDI) donor-acceptor hybrids. Moreover, we disclose, for the first time, results from the functional comparison of zipper and layer-by-layer (LBL) assembly as well as quartz crystal microbalance (QCM), atomic force microscopy (AFM), and molecular modeling data on zipper assembly. Compared to the previously reported blue and red NDIs, yellow NDIs are more pi-acidic, easier to reduce, and harder to oxidize. The optoelectronic matching achieved in yellow POP-NDIs is reflected in quantitative and long-lived photoinduced charge separation, comparable to their red and much better than their blue counterparts. The direct comparison of zipper and LBL assemblies reveals that yellow zippers generate more photocurrent than blue zippers as well as LBL photosystems. Continuing linear growth found in QCM measurements demonstrates that photocurrent saturation at the critical assembly thickness occurs because more charges start to recombine before reaching the electrodes and not because of discontinued assembly. The found characteristics, such as significant critical thickness, strong photocurrents, large fill factors, and, according to AFM images, smooth surfaces, are important for optoelectronic performance and support the existence of highly ordered architectures.

Attractive Forces between Charged Colloidal Particles Induced by Multivalent Ions Revealed by Confronting Aggregation and Direct Force Measurements

Interactions involving charged particles in the presence of multivalent ions are relevant in wide-range of phenomena, including condensation of nucleic acids, cement hardening, or water treatment. Here, we study such interactions by combining direct force measurements with atomic force microscopy (AFM) and aggregation studies with time-resolved light scattering for particles originating from the same colloidal suspension for the first time. Classical DLVO theory is found to be only applicable for monovalent and divalent ions. For ions of higher valence, charge inversion and additional non-DLVO attractive forces are observed. These attractive forces can be attributed to surface charge heterogeneities, which leads to stability ratios that are calculated from direct force measurements to be higher than the experimental ones. Ion-ion correlations are equally important as they induce the charge inversion in the presence of trivalent or tetravalent ions, and they enhance the surface charge heterogeneities. Such heterogeneities therefore play an essential role in controlling interactions in particle suspensions containing multivalent ions.

Investigating forces between charged particles in the presence of oppositely charged polyelectrolytes with the multi-particle colloidal probe technique.

Direct force measurements are used to obtain a comprehensive picture of interaction forces acting between charged colloidal particles in the presence of oppositely charged polyelectrolytes. These measurements are achieved by the multi-particle colloidal probe technique based on the atomic force microscope (AFM). This novel extension of the classical colloidal probe technique offers three main advantages. First, the technique works in a colloidal suspension with a huge internal surface area of several square meters, which simplifies the precise dosing of the small amounts of the polyelectrolytes needed and makes this approach less sensitive to impurities. Second, the particles are attached in-situ within the fluid cell, which avoids the formation of nanobubbles on the latex particles used. Third, forces between two similar particles from the same batch are being measured, which allows an unambiguous determination of the surface potential due to the symmetry of the system. Based on such direct force measurements involving positively and negatively charged latex particles and different polyelectrolytes, we find the following forces to be relevant. Repulsive electrostatic double-layer forces and attractive van der Waals forces as described by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) are both important in these systems, whereby the electrostatic forces dominate away from the isoelectric point (IEP), while at this point they vanish. Additional non-DLVO attractive forces are operational, and they have been identified to originate from the electrostatic interactions between the patch-charge heterogeneities of the adsorbed polyelectrolyte films. Highly charged polyelectrolytes induce strong patch-charge attractions, which become especially important at low ionic strengths and high molecular mass. More weakly charged polyelectrolytes seem to form more homogeneous films, whereby patch-charge attractions may become negligible. Individual bridging events could be only rarely identified from the retraction part of the force profiles, and therefore we conclude that bridging forces are unimportant in these systems.

Topologically Matching Supramolecular n/p-Heterojunction Architectures†

Matching matters when building supramolecular n/p-heterojunction photosystems on solid supports that excel with efficient photocurrent generation, important critical thickness, smooth surfaces, and flawless responsiveness to functional probes for the existence of operational intra- and interlayer recognition motifs.

Molecular-beam/surface-science apparatus for state-resolved chemisorption studies using pulsed-laser preparation

We describe a new apparatus that combines pulsed laser excitation in a molecular beam with surface-science methods for preparation of clean single-crystal surfaces and detection of adsorbates to enable state-selected studies of gas–surface reaction dynamics. Reactant molecules are prepared in specific vibrationally excited states via overtone pumping using tunable, narrow-band laser radiation. The collision-free environment of the molecular beam prevents relaxation of the prepared molecules before impact on the target surface and enables complete control over the collision energy and incidence angle. Chemisorption products are detected after a given deposition time by Auger electron spectroscopy. To achieve sufficient beam flux of state-selected reactant molecules for product detection by standard surface-science techniques, we use a high-intensity, short-pulse molecular-beam source matched to the low duty cycle of the pulsed lasers used in our experiments. We present the design and characterization of th...

Structure of adsorbed polyelectrolyte monolayers investigated by combining optical reflectometry and piezoelectric techniques.

Polyelectrolyte monolayers on solid substrates are studied with optical reflectivity and the quartz crystal microbalance (QCM). In particular, we investigate the adsorption of anionic poly(styrene sulfonate) (PSS) on amino-functionalized silica as well as cationic poly(allylamine hydrochloride) (PAH) and poly-L-lysine (PLL) on bare silica. By comparing the dry and wet masses measured on identical substrates with these two techniques, we obtain information on the layer thickness and water content of these layers. Monolayers typically feature an adsorbed dry mass of about 0.1-2 mg/m(2), a layer thickness of 0.5-2 nm, and a water content of 20-50%. One finds that the layer thickness increases with increasing concentrations of monovalent salts and polyelectrolytes.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10(-21) J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Predicting Aggregation Rates of Colloidal Particles from Direct Force Measurements

Direct force measurements between negatively charged colloidal latex particles of a diameter of 1 μm were carried out in aqueous solutions of various inorganic monovalent and multivalent cations with the multiparticle colloidal probe technique based on the atomic force microscope (AFM). The observed force profiles were rationalized within the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). In the presence of monovalent and divalent cations, this theory was capable to describe the force profiles correctly down to distances of a few nm. At shorter distances, however, a strong non-DLVO attraction was identified. For more highly charged cations, an additional and more long-ranged non-DLVO attractive force is observed, and it was interpreted by surface charge heterogeneities. On the basis of these force profiles, the aggregation rates, which were independently measured by light scattering, can be predicted relatively well. The main conclusion of this study is that, in the present system, direct force measurements do capture the principal interactions driving aggregation in colloidal suspensions.

Accurate predictions of forces in the presence of multivalent ions by Poisson-Boltzmann theory.

Forces between positively and negatively charged colloidal particles across aqueous salt solutions containing multivalent ions are measured directly with the atomic force microscope (AFM). The measurements are interpreted quantitatively with Poisson-Boltzmann (PB) theory. Thereby, the surface potentials and regulation properties of the particle surfaces are extracted from symmetric measurements between the same types of particles. This information is used to predict force profiles in the asymmetric situations involving different types of particles without any adjustable parameters. These predictions turn out to be very accurate, which demonstrates that the mean-field PB theory is reliable down to distances of about 5 nm. While various reports in the literature indicate that this theory should fail due to neglect of ion correlations, such effects seem important only at higher concentrations and smaller distances.