New mechanisms for chemistry at surfaces

It is becoming increasingly apparent that chemistry at surfaces, whether it be heterogeneous catalysis, semiconductors etching, or chemical vapor deposition, is controlled by much more than the nature and structure of the surface. Recent experiments that principally make use of molecular beam techniques have revealed that the energy at which an incident molecule collides with a surface can be the key factor in determining its reactivity with or on the surface. In addition, the collision energy of an incident particle has proven essential to the finding of new mechanisms for reaction or desorption of molecules at surfaces, collision-induced activation and collision-induced desorption. These phenomena are often responsible for the different surface chemistry observed under conditions of high reactant pressure, such as those present during a heterogeneous catalytic reaction, and of low pressure of reactants (< 10(-4) torr), such as those present in an ultrahigh vacuum surface science experiment. This knowledge of the microscopic origins of the effect of pressure on the chemistry at surfaces has allowed the development of a scheme to bypass the high-pressure requirement. Reactions that are normally observed only at high reactant pressures, and which are the ones most often of practical importance, can now be carried out in low-pressure, ultrahigh vacuum environments.     

Atomic-scale desorption through electronic and vibrational excitation mechanisms

The scanning tunneling microscope has been used to desorb hydrogen from hydrogen-terminated silicon (100) surfaces. As a result of control of the dose of incident electrons, a countable number of desorption sites can be created and the yield and cross section are thereby obtained. Two distinct desorption mechanisms are observed: (i) direct electronic excitation of the Si-H bond by field-emitted electrons and (ii) an atomic resolution mechanism that involves multiple-vibrational excitation by tunneling electrons at low applied voltages. This vibrational heating effect offers significant potential for controlling surface reactions involving adsorbed individual atoms and molecules.     

Surface analysis and atomic physics with slow positron beams

Recent advances in slow positron beam techniques are making it possible to study the interactions of low-energy positrons with gas molecules and solid surfaces and to measure the properties of free positronium atoms. New surface related results include the observation of surfaces with negative positron affinity and the thermionic emission of slow positronium atoms, low-energy positron diffraction measurements, and the sensitive detection of near-surface crystalline imperfections. Two recent successful experiments in atomic physics are the formation of the positronium negative ion and the optical excitation of positronium for high precisin spectroscopy. Prospects for a positron microscope and the study of exotic antimatter systems such as the two-component Fermi gas are based on the imminent possibility of enormous increases in the brightness and instantaneous intensity of positron beams.     

Mass spectrometry sampling under ambient conditions with desorption electrospray ionization

A new method of desorption ionization is described and applied to the ionization of various compounds, including peptides and proteins present on metal, polymer, and mineral surfaces. Desorption electrospray ionization (DESI) is carried out by directing electrosprayed charged droplets and ions of solvent onto the surface to be analyzed. The impact of the charged particles on the surface produces gaseous ions of material originally present on the surface. The resulting mass spectra are similar to normal ESI mass spectra in that they show mainly singly or multiply charged molecular ions of the analytes. The DESI phenomenon was observed both in the case of conductive and insulator surfaces and for compounds ranging from nonpolar small molecules such as lycopene, the alkaloid coniceine, and small drugs, through polar compounds such as peptides and proteins. Changes in the solution that is sprayed can be used to selectively ionize particular compounds, including those in biological matrices. In vivo analysis is demonstrated.     

Quantum States and atomic structure of silicon surfaces

The electronic and geometric structures of surfaces are closely related to each other. Conventional surface science techniques can study one or the other, but not both at the same time. Recent developments in scanning tunneling microscopy have made it possible to study simultaneously the electronic and geometric structure of Si(111) and Si(001) surfaces. Surface states can be atomically resolved in space and energy; thus the electronic structure of single atoms on surfaces can be studied in detail. The various surface states observed on silicon surfaces are found to derive from different atomic-scale features in the surface geometric structure. Scanning tunneling microscopy has now bridged the gap between electronic and geometric structure, providing a unique opportunity to obtain a better understanding of many surface processes at the atomic level.     

Molecular beam scattering from liquid surfaces

By means of controlled collisions of atoms and molecules with liquid surfaces, molecular beam experiments can be used to probe how gases stick to, rebound from, and exchange energy with molecules in the liquid phase. This report describes measurements of energy exchange in collisions between gases (neon, xenon, and sulfur hexafluoride) and polyatomic liquids (squalane and perfluoropolyether). Energy transfer depends critically on liquid composition and is more efficient for the hydrocarbon than for the perfluorinated ether.     

A simple kinetic model of polymer adsorption and desorption

A model of the desorption and adsorption of a polymer layer at a planar surface indicates a transition from exponential kinetics at high temperatures to nonexponential kinetics (stretched exponential with index one-half) at lower temperatures where these processes are diffusion-limited. Measurements of polystyrene desorption through polyisoprene overlayers show this predicted transition. Corroborative results are obtained for polystyrene desorption through polymethylmethacrylate overlayers. This identification of two distinct kinetic regimes suggests a unifying perspective from which to analyze polymer and biopolymer mobility at surfaces.     

Probing high-barrier pathways of surface reactions by scanning tunneling microscopy

The ability of scanning tunneling microscopy to probe the pathways of thermally activated high-barrier surface processes is frequently limited by competing low-barrier processes that can confuse measurement of the true initial and final configuration. We introduce an approach to circumvent this difficulty by driving the surface process with nanosecond laser heating. The method is applied to determine the pathway of recombinative desorption in the H/Si(001) system. The observed configuration of dangling bonds after laser heating reveals that the desorbed hydrogen molecules are not formed on single dimers, but rather from neighboring silicon dimers via an interdimer reaction pathway.     

Real-space observation of molecular motion induced by femtosecond laser pulses

Femtosecond laser irradiation is used to excite adsorbed CO molecules on a Cu110 surface; the ensuing motion of individual molecules across the surface is characterized on a site-to-site basis by in situ scanning tunneling microscopy. Adsorbate motion both along and perpendicular to the rows of the Cu110 surface occurs readily, in marked contrast to the behavior seen for equilibrium diffusion processes. The experimental findings for the probability and direction of the molecular motion can be understood as a manifestation of strong coupling between the adsorbates' lateral degrees of freedom and the substrate electronic excitation produced by the femtosecond laser radiation.     

Regenerative adsorption and removal of H2S from hot fuel gas streams by rare earth oxides

Sorbent materials that allow for high-temperature, regenerative desulfurization of fuel gas streams for the anode of a solid oxide fuel cell have been developed. Reversible adsorption of H2S on cerium and lanthanum oxide surfaces is demonstrated over many cycles at temperatures as high as 800 degrees C, on both fresh or presulfided sorbents, and at very high space velocities. The adsorption and desorption processes are very fast, and removal of H2S to sub-parts per million levels is achieved at very short (millisecond) contact times. Any type of sulfur-free gas, including water vapor, can be used to regenerate the sorbent surface. Preferably, the anode off-gas stream is used to sweep the desorbed H(2)S to a burner.     

Direct observation of chemical bond dynamics on surfaces

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.     

Cavitation and the interaction between macroscopic hydrophobic surfaces

The interaction in water of neutral hydrocarbon and fluorocarbon surfaces, prepared by Langmuir-Blodgett deposition of surfactant monolayers, has been investigated. The attraction between these hydrophobic surfaces can be measured at separations of 70 to 90 nanometers and thus is of considerably greater range than previously found. Spontaneous cavitation occurred as soon as the fluorocarbon surfaces were brought into contact but occurred between the hydrocarbon surfaces only after separation from contact. The very long range forces measured are a consequence of the metastability of water films between macroscopic hydrophobic surfaces. Thus the hydrophobic interaction between macroscopic surfaces may not be related to water structure in the same way that the hydrophobic effect between nonpolar molecules is related to water structure.     

Chemistry of molecular growth processes in flames

Chemical mechanisms of pyrolysis, growth, and oxidation processes in flames have traditionally been inferred from spatial profile measurements of species concentrations. Experimental investigations now include the detection of numerous minor species such as reactive radicals and intermediate hydrocarbons. In assessing a proposed mechanism important new constraints can be established when the detailed species profile data are combined with velocity and temperature measurements and analyzed to determine production and destruction rates for specific molecules. Recent results on hydrocarbon diffusion flames provide new information on the interplay between chemical and transport processes. These measurements have led to direct tests of proposed routes for the formation of aromatic hydrocarbons and the first, small soot particles. The inception chemistry of hydrocarbon growth reactions and initial particle formation is thought to control soot formation, flame radiation and energy transfer, and pollutant emission in combustion environments.     

Prooxidant states and tumor promotion

There is convincing evidence that cellular prooxidant states--that is, increased concentrations of active oxygen and organic peroxides and radicals--can promote initiated cells to neoplastic growth. Prooxidant states can be caused by different classes of agents, including hyperbaric oxygen, radiation, xenobiotic metabolites and Fenton-type reagents, modulators of the cytochrome P-450 electron-transport chain, peroxisome proliferators, inhibitors of the antioxidant defense, and membrane-active agents. Many of these agents are promoters or complete carcinogens. They cause chromosomal damage by indirect action, but the role of this damage in carcinogenesis remains unclear. Prooxidant states can be prevented or suppressed by the enzymes of the cellular antioxidant defense and low molecular weight scavenger molecules, and many antioxidants are antipromoters and anticarcinogens. Finally, prooxidant states may modulate the expression of a family of prooxidant genes, which are related to cell growth and differentiation, by inducing alterations in DNA structure or by epigenetic mechanisms, for example, by polyadenosine diphosphate-ribosylation of chromosomal proteins.     

New Opportunities in Synchrotron X-ray Crystallography

Several high-intensity synchrotron x-ray sources have been constructed over the past few years in the United States, West Germany, Great Britain, Japan, France, Italy, and the Soviet Union. Crystallographers have begun to use these facilities for experiments that take advantage of the characteristics of synchrotron radiation, namely, a broad distribution of wavelengths, high intensity, low divergence, strong polarization, and a pulsed time structure. In addition to more familiar diffraction experiments on single crystals and powdered samples, new types of crystallographic studies, for example, energy-dispersive and surface diffraction studies, have progressed rapidly with more general accessibility of synchrotron sources. These high-intensity sources allow diffraction experiments to be performed on very small crystals or on large biological molecules, and permit weak magnetic scattering to be detected Anomalous dispersion experiments can exploit he ability to vary the wavelength of the radiation, and the pulsed time structure of the beam makes possible fast time-resolved experiments. Because of the availability of synchrotron x-radiation, these and other kinds of experiments will be in the forefront of crystallographic research for the next several years.     

Theoretical studies of the energetics and dynamics of chemical reactions

Computational studies of basic chemical processes not only provide numbers for comparison with experiment or for use in modeling complex chemical phenomena such as combustion, but also provide insight into the fundamental factors that govern molecular structure and change which cannot be obtained from experiment alone. We summarize the results of three case studies, on HCO, OH + H(2), and O + C(2)H(2), which illustrate the range of problems that can be addressed by using modern theoretical techniques. In all cases, the potential energy surfaces were characterized by using ab initio electronic structure methods. Collisions between molecules leading to reaction or energy transer were described with quantum dynamical methods (HCO), classical trajectory techniques (HCO and OH + H(2)), and statistical methods (HCO, OH + H(2), and O + C(2)H(2)). We can anticipate dramatic increases in the scope of this work as new generations of computers are introduced and as new chemistry software is developed to exploit these computers.     

Molecular recognition by self-assembled monolayers of cavitand receptors

It is shown by angle-resolved x-ray photoelectron spectroscopy that cavitands derived from resorcin[4]arenes provided with four dialkylsulfide chains form stable monolayers on gold surfaces that are well organized by self-assembly. The cavitand headgroups at the surface of the resorcin[4]arene monolayer act as molecular recognition sites for small organic molecules with remarkable selectivity for perchloroethylene (C(2)Cl(4)). Comparative thermal desorption experiments indicate binding sites with high interaction energies of C(2)Cl(4) at the surface of the resorcin[4]arene monolayers. Fast and reversible "host-guest" interactions were found by the monitoring of extremely small mass changes (in the nanogram range) with a quartz microbalance oscillator provided with gold electrodes coated by resorcin[4]arene monolayers.     

Surface spectroscopies with synchrotron radiation

A variety of photoelectron spectroscopies using synchrotron radiation have been devised to study solid surfaces. Measurements of the energies and angular distributions of electrons photoemitted from valence levels yield detailed information on surface electronic states and the chemical bonding of adsorbed atoms and molecules. Core level studies yield surface atom positions and molecular orientations. Some highlights of recent research are presented here. The capabilities of the techniques will be extended by the forthcoming generation of new storage rings dedicated to the production of synchrotron radiation.     

Arctic air pollution: origins and impacts

Notable warming trends have been observed in the Arctic. Although increased human-induced emissions of long-lived greenhouse gases are certainly the main driving factor, air pollutants, such as aerosols and ozone, are also important. Air pollutants are transported to the Arctic, primarily from Eurasia, leading to high concentrations in winter and spring (Arctic haze). Local ship emissions and summertime boreal forest fires may also be important pollution sources. Aerosols and ozone could be perturbing the radiative budget of the Arctic through processes specific to the region: Absorption of solar radiation by aerosols is enhanced by highly reflective snow and ice surfaces; deposition of light-absorbing aerosols on snow or ice can decrease surface albedo; and tropospheric ozone forcing may also be contributing to warming in this region. Future increases in pollutant emissions locally or in mid-latitudes could further accelerate global warming in the Arctic.     

In situ interfacial mass detection with piezoelectric transducers

The converse piezoelectric effect, in which an electric field applied across a piezoelectric material induces a stress in that material, has spurred many recent developments in mass measurement techniques. These methods commonly rely on the changes in the vibrational resonant frequency of piezoelectric quartz oscillators that result from changes in mass on the surface of the oscillator. The dependence of frequency on mass has been exploited extensively for mass measurements in vacuum or gas phase, for example, thickness monitors for thin-film preparation and sensors for chemical agents. Advances in piezoelectric methodology in the last decade now allow dynamic measurements of minute mass changes (< 10(-9) grams per square centimeter) at surfaces, thin films, and electrode interfaces in liquid media as well. Mass measurements associated with a diverse collection of interfacial processes can be readily performed, including chemical and biological sensors, reactions catalyzed by enzymes immobilized on surfaces, electron transfer at and ion exchange in thin polymer films, and doping reactions of conducting polymers.