The photon‐induced reactions of chemisorbed CH₃Br on Pt{111}

The photochemistry of chemisorbed CH3Br on Pt{111} has been investigated using high resolution electron energy loss spectroscopy (HREELS) and thermal desorption. The primary photon‐induced reaction involves the cleavage of the C–Br bond, giving rise to chemisorbed CH3 and Br, both of which can be identified in HREELS. From the angular dependence of the loss peaks, the symmetry of the CH3 surface complex is shown to be C3v. HBr can also be identified in subsequent thermal desorption. Experiments performed directly with HBr on Pt{111} indicate that molecular HBr adsorbs dissociatively on this surface. This result, in combination with observations of the C–H vibrational mode as a function of temperature, shows that the production of HBr arises from a secondary surface reaction between Br and CHx fragments. Based on the wavelength dependence of the fragmentation cross section and the photoemission spectrum of adsorbed CH3Br the primary photon‐induced reaction to a charge transfer excitation is ascribed

Electromagnetic Momentum in Dispersive Dielectric Media

When the effects of dispersion are included, neither the Abraham nor the Minkowski expression for electromagnetic momentum in a dielectric medium gives the correct recoil momentum for absorbers or emitters of radiation. The total momentum density associated with a field in a dielectric medium has three contributions: (i) the Abraham momentum density of the field, (ii) the momentum density associated with the Abraham force, and (iii) a momentum density arising from the dispersive part of the response of the medium to the field, the latter having a form evidently first derived by D.F. Nelson [Phys. Rev. A 44, 3985 (1991)]. All three contributions are required for momentum conservation in the recoil of an absorber or emitter in a dielectric medium. We consider the momentum exchanged and the force on a polarizable particle (e.g., an atom or a small dielectric sphere) in a host dielectric when a pulse of light is incident upon it, including the dispersion of the dielectric medium as well as a dispersive component in the response of the particle to the field. The force can be greatly increased in slow-light dielectric media.Comment: 9 pages. To be published by Optics Communication

Laser-modified one- and two-photon absorption:Expanding the scope of optical nonlinearity

It is shown that conventional one-photon and two-photon absorption processes can be made subject to nonlinear optical control, in each case significantly modifying the efficiency of absorption, through the effect of a secondary, off-resonant stimulus laser beam. The mechanistic origin of these laser-modified absorption processes, in which the stimulus beam emerges unchanged, is traced to higher-order terms in standard perturbation treatments. These normally insignificant terms become unusually prominent when the secondary optical stimulus is moderately intense. Employing a quantum formulation, the effects of the stimulus beam on one-photon and two-photon absorption are analyzed, and calculations are performed to determine the degree of absorption enhancement, and the form of spectral manifestation, under various laser intensities. The implications of differences in selection rules are also considered and exemplified, leading to the identification of dark states that can be populated as a result of laser-modified absorption. Attention is also drawn to the possibility of quantum nondemolition measurements, based on such a form of optical nonlinearity

Laser-controlled fluorescence in two-level systems

The ability to modify the character of fluorescent emission by a laser-controlled, optically nonlinear process has recently been shown theoretically feasible, and several possible applications have already been identified. In operation, a pulse of off-resonant probe laser beam, of sufficient intensity, is applied to a system exhibiting fluorescence, during the interval of excited- state decay following the initial excitation. The result is a rate of decay that can be controllably modified, the associated changes in fluorescence behavior affording new, chemically specific information. In this paper, a two-level emission model is employed in the further analysis of this all-optical process; the results should prove especially relevant to the analysis and imaging of physical systems employing fluorescent markers, these ranging from quantum dots to green fluorescence protein. Expressions are presented for the laser-controlled fluorescence anisotropy exhibited by samples in which the fluorophores are randomly oriented. It is also shown that, in systems with suitably configured electronic levels and symmetry properties, fluorescence emission can be produced from energy levels that would normally decay nonradiatively. © 2010 American Chemical Society

Influence of biomass combustion emissions on the distribution of acidic trace gases over the southern Pacific basin during austral springtime

This paper describes the large-scale distributions of HNO3, HCOOH, and CH3COOH over the central and South Pacific basins during the Pacific Exploratory Mission-Tropics (PEM-Tropics) in austral springtime. Because of the remoteness of this region from continental areas, low part per trillion by volume (pptv) mixing ratios of acidic gases were anticipated to be pervasive over the South Pacific basin. However, at altitudes of 2–12 km over the South Pacific, air parcels were encountered frequently with significantly enhanced mixing ratios (up to 1200 pptv) of acidic gases. Most of these air parcels were centered in the 3–7 km altitude range and occurred within the 15°−65°S latitudinal band. The acidic gases exhibited an overall general correlation with CH3Cl, PAN, and O3, suggestive of photochemical and biomass burning sources. There was no correlation or trend of acidic gases with common industrial tracer compounds (e.g., C2Cl4 or CH3CCl3). The combustion emissions sampled over the South Pacific basin were relatively aged exhibiting C2H2/CO ratios in the range of 0.2–2.2 pptv/ppbv. The relationships between acidic gases and this ratio were similar to what was observed in aged air parcels (i.e., \u3e3–5 days since they were over a continental area) over the western North Pacific during the Pacific Exploratory Mission-West Phases A and B (PEM-West A and B). In the South Pacific marine boundary layer a median C2H2/CO ratio of 0.6 suggested that this region was generally not influenced by direct inputs of biomass combustion emissions. Here we observed the lowest mixing ratios of acidic gases, with median values of 14 pptv for HNO3, 19 pptv for HCOOH, and 18 pptv for CH3COOH. These values were coincident with low mixing ratios of NOx(\u3c10 pptv), CO (≈50 parts per billion by volume (ppbv)), O3 (\u3c 20 ppbv), and long-lived hydrocarbons (e.g., C2H6 \u3c300 pptv). Overall, the PEM-Tropics data suggest an important influence of aged biomass combustion emissions on the distributions of acidic gases over the South Pacific basin in austral springtime

Surface diffusion of K on Pd{111}: Coverage dependence of the diffusion coefficient determined with the Boltzmann–Matano method

The surface diffusion of potassium on Pd{111} has been studied with photoelectron emission microscopy (PEEM) for coverages up to one monolayer. The coverage dependence of the chemical diffusion coefficient is determined by analysis of the concentration profiles obtained from the PEEM images with the Boltzmann–Matano method. The diffusion coefficient, D, decreases with increasing coverage but a local maximum is found at a coverage of Θ≈0.5 ML. The values of D at low coverages (Θ<0.3 ML) agree well with those obtained in a previous investigation for Θ≈0.12 ML. The maximum in D is interpreted in terms of an order–disorder phase transition in the adsorbed layer

In situ bioremediation: A network model of diffusion and flow in granular porous media

In situ bioremediation is a potentially expedient, permanent and cost- effective means of waste site decontamination. However, permeability reductions due to the transport and deposition of native fines or due to excessive microorganism populations may severely inhibit the injection of supplemental oxygen in the contamination zone. To help understand this phenomenon, we have developed a micro-mechanical network model of flow, diffusion and particle transport in granular porous materials. The model differs from most similar models in that the network is defined by particle positions in a numerically-generated particle array. The model is thus widely applicable to computing effective transport properties for both ordered and realistic random porous media. A laboratory-scale apparatus to measure permeability reductions has also been designed, built and tested

Chiral discrimination in optical trapping and manipulation

When circularly polarized light interacts with chiral molecules or nanoscale particles powerful symmetry principles determine the possibility of achieving chiral discrimination, and the detailed form of electrodynamic mechanisms dictate the types of interaction that can be involved. The optical trapping of molecules and nanoscale particles can be described in terms of a forward-Rayleigh scattering mechanism, with trapping forces being dependent on the positioning within the commonly non-uniform intensity beam profile. In such a scheme, nanoparticles are commonly attracted to local potential energy minima, ordinarily towards the centre of the beam. For achiral particles the pertinent material response property usually entails an electronic polarizability involving transition electric dipole moments. However, in the case of chiral molecules, additional effects arise through the engagement of magnetic counterpart transition dipoles. It emerges that, when circularly polarized light is used for the trapping, a discriminatory response can be identified between left- and right-handed polarizations. Developing a quantum framework to accurately describe this phenomenon, with a tensor formulation to correctly represent the relevant molecular properties, the theory leads to exact analytical expressions for the associated energy landscape contributions. Specific results are identified for liquids and solutions, both for isotropic media and also where partial alignment arises due to a static electric field. The paper concludes with a pragmatic analysis of the scope for achieving enantiomer separation by such methods