Institute for Atomic and Molecular Physics

We describe a global optimization technique using `basin-hopping' in which the potential energy surface is transformed into a collection of interpenetrating staircases. This method has been designed to exploit the features which recent work suggests must be present in an energy landscape for efficient relaxation to the global minimum. The transformation associates any point in configuration space with the local minimum obtained by a geometry optimization started from that point, effectively removing transition state regions from the problem. However, unlike other methods based upon hypersurface deformation, this transformation does not change the global minimum. The lowest known structures are located for all Lennard-Jones clusters up to 110 atoms, including a number that have never been found before in unbiased searches.

In principle, the temporal beating of superposed high harmonics obtained by focusing a femtosecond laser pulse in a gas jet can produce a train of very short intensity spikes, depending on the relative phases of the harmonics. We present a method to measure such phases through two-photon, two-color photoionization. We found that the harmonics are locked in phase and form a train of 250-attosecond pulses in the time domain. Harmonic generation may be a promising source for attosecond time-resolved measurements.

Recent developments in photovoltaic materials have led to continual improvements in their efficiency. We review the electrical characteristics of 16 widely studied geometries of photovoltaic materials with efficiencies of 10 to 29%. Comparison of these characteristics to the fundamental limits based on the Shockley-Queisser detailed-balance model provides a basis for identifying the key limiting factors, related to efficient light management and charge carrier collection, for these materials. Prospects for practical application and large-area fabrication are discussed for each material.

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.

We describe the development of solar water-splitting cells comprising earth-abundant elements that operate in near-neutral pH conditions, both with and without connecting wires. The cells consist of a triple junction, amorphous silicon photovoltaic interfaced to hydrogen- and oxygen-evolving catalysts made from an alloy of earth-abundant metals and a cobalt|borate catalyst, respectively. The devices described here carry out the solar-driven water-splitting reaction at efficiencies of 4.7% for a wired configuration and 2.5% for a wireless configuration when illuminated with 1 sun (100 milliwatts per square centimeter) of air mass 1.5 simulated sunlight. Fuel-forming catalysts interfaced with light-harvesting semiconductors afford a pathway to direct solar-to-fuels conversion that captures many of the basic functional elements of a leaf.

The scattering from metal nanoparticles near their localized plasmon resonance is a promising way of increasing the light absorption in thin-film solar cells. Enhancements in photocurrent have been observed for a wide range of semiconductors and solar cell configurations. We review experimental and theoretical progress that has been made in recent years, describe the basic mechanisms at work, and provide an outlook on future prospects in this area.

Numerical simulations of homogeneous crystal nucleation with a model for globular proteins with short-range attractive interactions showed that the presence of a metastable fluid-fluid critical point drastically changes the pathway for the formation of a crystal nucleus. Close to this critical point, the free-energy barrier for crystal nucleation is strongly reduced and hence, the crystal nucleation rate increases by many orders of magnitude. Because the location of the metastable critical point can be controlled by changing the composition of the solvent, the present work suggests a systematic approach to promote protein crystallization.

Using a home-built frictional force microscope that is able to detect forces in three dimensions with a lateral force resolution down to 15 pN, we have studied the energy dissipation between a tungsten tip sliding over a graphite surface in dry contact. By measuring atomic-scale friction as a function of the rotational angle between two contacting bodies, we show that the origin of the ultralow friction of graphite lies in the incommensurability between rotated graphite layers, an effect proposed under the name of "superlubricity" [Phys. Rev. B 41, 11 837 (1990)]].

The trade-off between physical adsorption capacity and selectivity of porous materials is a major barrier for efficient gas separation and purification through physisorption. We report control over pore chemistry and size in metal coordination networks with hexafluorosilicate and organic linkers for the purpose of preferential binding and orderly assembly of acetylene molecules through cooperative host-guest and/or guest-guest interactions. The specific binding sites for acetylene are validated by modeling and neutron powder diffraction studies. The energies associated with these binding interactions afford high adsorption capacity (2.1 millimoles per gram at 0.025 bar) and selectivity (39.7 to 44.8) for acetylene at ambient conditions. Their efficiency for the separation of acetylene/ethylene mixtures is demonstrated by experimental breakthrough curves (0.73 millimoles per gram from a 1/99 mixture).

In order to introduce flexibility into the simple point-charge (SPC) water model, the impact of the intramolecular degrees of freedom on liquid properties was systematically studied in this work as a function of many possible parameter sets. It was found that the diffusion constant is extremely sensitive to the equilibrium bond length and that this effect is mainly due to the strength of intermolecular hydrogen bonds. The static dielectric constant was found to be very sensitive to the equilibrium bond angle via the distribution of intermolecular angles in the liquid: A larger bond angle will increase the angle formed by two molecular dipoles, which is particularly significant for the first solvation shell. This result is in agreement with the work of Hochtl et al. [J. Chem. Phys. 109, 4927 (1998)]. A new flexible simple point-charge water model was derived by optimizing bulk diffusion and dielectric constants to the experimental values via the equilibrium bond length and angle. Due to the large sensitivities, the parametrization only slightly perturbs the molecular geometry of the base SPC model. Extensive comparisons of thermodynamic, structural, and kinetic properties indicate that the new model is much improved over the standard SPC model and its overall performance is comparable to or even better than the extended SPC model.

Time-resolved, pulsed terahertz spectroscopy has developed into a powerful tool to study charge carrier dynamics in semiconductors and semiconductor structures over the past decades. Covering the energy range from a few to about 100 meV, terahertz radiation is sensitive to the response of charge quasiparticles, e.g., free carriers, polarons, and excitons. The distinct spectral signatures of these different quasiparticles in the THz range allow their discrimination and characterization using pulsed THz radiation. This frequency region is also well suited for the study of phonon resonances and intraband transitions in low-dimensional systems. Moreover, using a pump-probe scheme, it is possible to monitor the nonequilibrium time evolution of carriers and low-energy excitations with sub-ps time resolution. Being an all-optical technique, terahertz time-domain spectroscopy is contact-free and noninvasive and hence suited to probe the conductivity of, particularly, nanostructured materials that are difficult or impossible to access with other methods. The latest developments in the application of terahertz time-domain spectroscopy to bulk and nanostructured semiconductors are reviewed.

A general method to coat colloids with silica is described. The amphiphilic, nonionic polymer poly(vinylpyrrolidone) (PVP) was adsorbed to various colloidal particles such as small gold colloids, gold-shell silica-core particles, small and large silver colloids, boehmite rods, gibbsite platelets, and positively or negatively charged polystyrene. After this functionalization the stabilized particles could be transferred to a solution of ammonia in ethanol and directly coated with smooth and homogeneous silica shells of variable thickness by addition of tetraethoxysilane in a seeded growth process. The length of the polymer used strongly influences the stability of the colloids and the homogeneity and smoothness of the initial silica coating. This method is especially useful for colloidal particles that cannot be covered directly with SiO2 by a Stöber-like growth process. Compared to methods known from the literature for the coating of such particles, this new method is faster and requires neither the use of silane coupling agents nor a precoating step with sodium silicate, which is poorly reproducible.

Progress in the area of MHD stability and disruptions, since the publication of the 1999 ITER Physics Basis document (1999 Nucl. Fusion 39 2137-2664), is reviewed. Recent theoretical and experimental research has made important advances in both understanding and control of MHD stability in tokamak plasmas. Sawteeth are anticipated in the ITER baseline ELMy H-mode scenario, but the tools exist to avoid or control them through localized current drive or fast ion generation. Active control of other MHD instabilities will most likely be also required in ITER. Extrapolation from existing experiments indicates that stabilization of neoclassical tearing modes by highly localized feedback-controlled current drive should be possible in ITER. Resistive wall modes are a key issue for advanced scenarios, but again, existing experiments indicate that these modes can be stabilized by a combination of plasma rotation and direct feedback control with non-axisymmetric coils. Reduction of error fields is a requirement for avoiding non-rotating magnetic island formation and for maintaining plasma rotation to help stabilize resistive wall modes. Recent experiments have shown the feasibility of reducing error fields to an acceptable level by means of non-axisymmetric coils, possibly controlled by feedback. The MHD stability limits associated with advanced scenarios are becoming well understood theoretically, and can be extended by tailoring of the pressure and current density profiles as well as by other techniques mentioned here. There have been significant advances also in the control of disruptions, most notably by injection of massive quantities of gas, leading to reduced halo current fractions and a larger fraction of the total thermal and magnetic energy dissipated by radiation. These advances in disruption control are supported by the development of means to predict impending disruption, most notably using neural networks. In addition to these advances in means to control or ameliorate the consequences of MHD instabilities, there has been significant progress in improving physics understanding and modelling. This progress has been in areas including the mechanisms governing NTM growth and seeding, in understanding the damping controlling RWM stability and in modelling RWM feedback schemes. For disruptions there has been continued progress on the instability mechanisms that underlie various classes of disruption, on the detailed modelling of halo currents and forces and in refining predictions of quench rates and disruption power loads. Overall the studies reviewed in this chapter demonstrate that MHD instabilities can be controlled, avoided or ameliorated to the extent that they should not compromise ITER operation, though they will necessarily impose a range of constraints.

Erbium doped materials are of great interest in thin film integrated optoelectronic technology, due to their Er3+intra-4f emission at 1.54 μm, a standard telecommunication wavelength. Er-doped dielectric thin films can be used to fabricate planar optical amplifiers or lasers that can be integrated with other devices on the same chip. Semiconductors, such as silicon, can also be doped with erbium. In this case the Er may be excited through optically or electrically generated charge carriers. Er-doped Si light-emitting diodes may find applications in Si-based optoelectronic circuits. In this article, the synthesis, characterization, and application of several different Er-doped thin film photonic materials is described. It focuses on oxide glasses (pure SiO2, phosphosilicate, borosilicate, and soda-lime glasses), ceramic thin films (Al2O3,Y2O3, LiNbO3), and amorphous and crystalline silicon, all doped with Er by ion implantation. MeV ion implantation is a technique that is ideally suited to dope these materials with Er as the ion range corresponds to the typical micron dimensions of these optical materials. The role of implantation defects, the effect of annealing, concentration dependent effects, and optical activation are discussed and compared for the various materials.

We propose a novel approach that allows efficient numerical simulation of systems consisting of flexible chain molecules. The method is especially suitable for the numerical simulation of dense chain systems and monolayers. A new type of Monte Carlo move is introduced that makes it possible to carry out large scale conformational changes of the chain molecule in a single trial move. Our scheme is based on the selfavoiding random walk algorithm of Rosenbluth and Rosenbluth. As an illustration, we compare the results of a calculation of mean-square end to end lengths for single chains on a two-dimensional square lattice with corresponding data gained from other simulations.

A preference for ethane Industrial production of ethylene requires its separation from ethane in a cryogenic process that consumes large amounts of energy. An alternative would be differential sorption in microporous materials. Most of these materials bind ethylene more strongly that ethane, but adsorption of ethane would be more efficient. Li et al. found that a metal-organic framework containing iron-peroxo sites bound ethane more strongly than ethylene and could be used to separate the gases at ambient conditions. Science , this issue p. 443

Imaging mass spectrometry combines the chemical specificity and parallel detection of mass spectrometry with microscopic imaging capabilities. The ability to simultaneously obtain images from all analytes detected, from atomic to macromolecular ions, allows the analyst to probe the chemical organization of a sample and to correlate this with physical features. The sensitivity of the ionization step, sample preparation, the spatial resolution, and the speed of the technique are all important parameters that affect the type of information obtained. Recently, significant progress has been made in each of these steps for both secondary ion mass spectrometry (SIMS) and matrix-assisted laser desorption/ionization (MALDI) imaging of biological samples. Examples demonstrating localization of proteins in tumors, a reduction of lamellar phospholipids in the region binding two single celled organisms, and sub-cellular distributions of several biomolecules have all contributed to an increasing upsurge in interest in imaging mass spectrometry. Here we review many of the instrumental developments and methodological approaches responsible for this increased interest, compare and contrast the information provided by SIMS and MALDI imaging, and discuss future possibilities.

Cavity ring-down (CRD) spectroscopy is a direct absorption technique, which can be performed with pulsed or continuous light sources and has a significantly higher sensitivity than obtainable in conventional absorption spectroscopy. The CRD technique is based upon the measurement of the rate of absorption rather than the magnitude of absorption of a light pulse confined in a closed optical cavity with a high Q factor. The advantage over normal absorption spectroscopy results from, firstly, the intrinsic insensitivity to light source intensity fluctuations and, secondly, the extremely long effective path lengths (many kilometres) that can be realized in stable optical cavities. In the last decade, it has been shown that the CRD technique is especially powerful in gas-phase spectroscopy for measurements of either strong absorptions of species present in trace amounts or weak absorptions of abundant species. In this review, we emphasize the various experimental schemes of CRD spectroscopy, and we show how these schemes can be used to obtain spectroscopic information on atoms, molecules, ions and clusters in many environments such as open air, static gas cells, supersonic expansions, flames and discharges.

The effects of ions on bulk properties of liquid water, such as viscosity, have suggested that ions alter water's hydrogen-bonding network. We measured the orientational correlation time of water molecules in Mg(ClO4)2, NaClO4, and Na2SO4 solutions by means of femtosecond pump-probe spectroscopy. The addition of ions had no influence on the rotational dynamics of water molecules outside the first solvation shells of the ions. This result shows that the presence of ions does not lead to an enhancement or a breakdown of the hydrogen-bond network in liquid water.

We develop fundamental design principles for increasing the efficiency of solar cells using light trapping by scattering from metal nanoparticles. We show that cylindrical and hemispherical particles lead to much higher path length enhancements than spherical particles, due to enhanced near-field coupling, and that the path length enhancement for an electric point dipole is even higher than the Lambertian value. Silver particles give much higher path length enhancements than gold particles. The scattering cross section of the particles is very sensitive to the thickness of a spacer layer at the substrate, which provides additional tunability in the design of particle arrays.