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At least 55 records · Page 3

Excited-State Charge Distribution of a Donor–π–Acceptor Zn Porphyrin Probed by N K-Edge Transient Absorption Spectroscopy

Zinc porphyrin solar cell dyes with donor-π–acceptor architectures combine light absorber (π), electron-donor, and electron-acceptor moieties inside a single molecule with atomic precision. The donor-π–acceptor design promotes the separation of charge carriers following optical excitation. Here, we probe the excited-state electronic structure within such molecules by combining time-resolved X-ray absorption spectroscopy at the N K-edge with first-principles time-dependent density functional theory (TD-DFT) calculations. Furthermore, customized Zn porphyrins with strong-donor triphenylamine groups or weak-donor tri-tert-butylbenzene groups were synthesized. Energetically well-separated N K-edge absorption features simultaneously probe the excited-state electronic structure from the perspectives of the macrocycle and triphenylamine N atoms. New absorption transitions between the macrocycle N atoms and the excited-state HOMO vacancy are observed, and the triphenylamine associated absorption feature blue-shifts, consistent with partial oxidation of the donor groups in the excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mapping hidden space-charge distributions across crystalline metal oxide/group IV semiconductor interfaces

The electronic structures of semiconducting heterojunctions are critically dependent on composition including the presence and concentrations of dopants, both intended and unintended. Dopant profiles in the interfacial region can have major effects on band energies which in turn drive transport properties. Here, in this study, we use core-level photoelectron line shapes excited with hard x rays to extract information about electric fields resulting from internal charge transfer in epitaxial La 0.03 Sr 0.97 Zr x Ti 1–x O 3 /Ge(001) (0.1≤x≤0.7) heterostructures. Experiments were carried out for heterojunctions involving both n- and p-type Ge substrates. These heterojunctions were not amenable to electronic characterization of all regions by transport measurements because the doped substrates act as electrical shunts, precluding probing the more resistive films and masking interface conductivity. However, the core-level line shapes were found to be a rich source of information on built-in potentials that exist throughout the heterostructure, and yielded valuable insight into the impact of band bending on band alignment at the buried interfaces. The electronic effects expected for Ge with uniform n- and p-type doping are eclipsed by those of unintended oxygen dopants in the Ge near the interface. This study illustrates the power of hard x-ray photoemission spectroscopy and related modeling to determine electronic structure in material systems for which insight from traditional transport measurements is limited.

36 MATERIALS SCIENCE↗

Charge distribution in lightning flashes

Four VHF receivers about 10 km apart were used to detect three-dimensional lightning VHF sources during active thunderstorms. A computer implemented algorithm was used to determine the difference in the time of arrival (DTOA) between the VHF pulses. The three-dimensional source locations determined from the DTOA were correlated with ground electric field measurements (0.1 Hz to 1.5 MHz). Four cloud to ground (CG) and three intracloud (IC) flashes, selected randomly, were studied. A point charge model was used to determine the charge being removed during the different phases of CG and IC flashes. It was determined that return strokes lowered between 24.1 and 3.6 coulombs of negative charge to ground from heights between 10.5 and 5.8 km above MSL. The interstroke process after the first return stroke in a CG flash lowered between 3.4 and 0.9 coulombs of negative charge between the heights of 14.2 (near the cloud tops) to heights of 5.8 km (near the beginning of the leader-return stroke process).

Rustan, P. L.↗

Stable dielectric charge distributions from field enhancement of secondary mission

The emission of secondary electrons from dielectrics subject to numerous effects of electric field which are experimentally difficult to control is discussed. Measurements are reported using pulse techniques such that local fields do not build to significant levels, but measurements with fields present are also of interest. A specific series of measurements under controlled conditions are described and their implications in terms of fields, magnitude and angle, near the dielectric surface were examined. The measurements were made for a charged fluorinated-ethylene-propylene surface near a grounded aluminum half-round resting on the surface. The geometry produced a stable surface-charge gradient being controlled by a strongly enhanced secondary emission for which a model is constructed. Observations of surface flashovers under various conditions confirm the predictions of some scaling exercises.

Robinson, J. W.↗

Mars Dust: Characterization of Particle Size and Electrostatic Charge Distributions

Some of the latest pictures of Mars surface sent by NASA s Spirit rover in early January, 2004, show very cohesive, mud-like dust layers. Significant amounts of dust clouds are present in the atmosphere of Mars. NASA spacecraft missions to Mars confirmed hypotheses from telescopic work that changes observed in the planet s surface markings are caused by wind-driven redistribution of dust. In these dust storms, particles with a wide range of diameters (< 1 m to 50 m) are a serious problem to solar cells, spacecraft, and spacesuits. Dust storms may cover the entire planet for an extended period of time. It is highly probable that the particles are charged electrostatically by triboelectrification and by UV irradiation.

Mazumder, M. K.↗

Mars Dust: Characterization of Particle Size and Electrostatic Charge Distribution

Some of the latest pictures of Mars surface sent by NASA's Spirit rover in early January, 2004, show very cohesive, "mud-like" dust layers. Significant amounts of dust clouds are present in the atmosphere of Mars [1-4]. NASA spacecraft missions to Mars confirmed hypotheses from telescopic work that changes observed in the planet's surface markings are caused by wind-driven redistribution of dust. In these dust storms, particles with a wide range of diameters (less than 1 micrometer to 50 micrometers) are a serious problem to solar cells, spacecraft, and spacesuits. Dust storms may cover the entire planet for an extended period of time [5]. It is highly probable that the particles are charged electrostatically by triboelectrification and by UV irradiation.

Mazumder, M. K.↗

Erratum to: Measurements of higher-order cumulants of multiplicity and net-electric charge distributions in inelastic proton-proton interactions by NA61/SHINE

This Erratum replaces, due to a discovery of coding mistakes, the following quantities: κ 3 /κ 1 of the h + − h − distribution presented in Fig. 6 and Table 6, κ 4 listed in Table 4, and $\hat{C}$ 4 presented in Fig. 7 and Table 5. All mentioned figures and tables were updated.

High-Energy Particle Collision Data Analysis↗

Temperature Dependence of Charge Distributions and Carrier Mobility in an Undoped Si/SiGe Heterostructure

Capacitance–voltage (C–V ) characteristics and carrier transport properties of 2-D electron gases (2DEGs) in an undoped Si/SiGe heterostructure at T = 4 – 35 K are presented here. In this work, two capacitance plateaus due to density saturation of the 2DEG in the buried Si quantum well (QW) are observed and explained by a model of surface tunneling. The peak mobility at 4 K is 4.1 × 10 5 cm 2 /V·s and enhanced by a factor of 1.97 at an even lower carrier density compared to the saturated carrier density, which is attributed to the effect of remote carrier screening. At T = 35 K, the mobility enhancement with a factor of 1.35 is still observed, which suggests the surface tunneling is still dominant.

42 ENGINEERING↗

Electronic levels and charge distribution near the interface of nickel

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

Waber, J. T.↗

Nuclear and ionic charge distribution experiment on ISEE-1 and ISEE-3

The experimental work carried out under this contract is a continuation of that originally performed under Contracts NAS5-20062 and NAS5-26739. The data analyzed are from the Max-Planck Institut/Univ. of Maryland experiment on ISEE-1 and ISEE-3. Each spacecraft experiment consists of a nearly identical set of three sensors (designated the ULECA, ULEWAT, and ULEZEQ sensors) designed to measure the energy spectra and composition of suprathermal and energetic ions over a broad energy range (less than 3 keV/e to more than 20 MeV/nucleon). Since the launch of ISEE's 2 and 3, the MPI/Univ. of Maryland experiments have generally performed as expected except for a partial failure of the ULEWAT sensor on ISEE-1 in August 1978. A number of scientific studies have either been completed, initiated or are at various stages of completion. A brief summary of Primary Results is given, followed by a more detailed summary of the major accomplishments at the Univ. of Maryland.

Gloeckler, G.↗

Measurement of Mars Dust Particle Size and Electrostatic Charge Distributions Using the E-SPART Analyzer

There are strong indications that dust is of great importance on Mars. Dust appears to have both long-term effects on the surface geologic evolution as well as on the aeolian processes in the present climate conditions. Early spacecraft missions confirmed hypotheses from telescopic work that changes observed in the planet s surface markings are caused by wind-driven redistribution of dust. Suspended dust is known to alter the atmospheric thermal structure and circulation as well as to obscure our ability for remote observation of the planet s surface, especially during the occasional development of larger, planet-encircling dust storms which occur on average once every three Martian years.

Mazumder, M. K.↗

Modeling of Optical Waveguide Poling and Thermally Stimulated Discharge (TSD) Charge and Current Densities for Guest/Host Electro Optic Polymers

A charge density and current density model of a waveguide system has been developed to explore the effects of electric field electrode poling. An optical waveguide may be modeled during poling by considering the dielectric charge distribution, polarization charge distribution, and conduction charge generated by the poling field. These charge distributions are the source of poling current densities. The model shows that boundary charge current density and polarization current density are the major source of currents measured during poling and thermally stimulated discharge These charge distributions provide insight into the poling mechanisms and are directly related to E(sub A), and, alpha(sub r). Initial comparisons with experimental data show excellent correlation to the model results.

Watson, Michael D.↗

Can Polyelectrolyte Mechanical Properties be Directly Modulated by an Electric Field? A Molecular Dynamics Study

Multifunctionality in polymers facilitates their application in emerging technologies. Electrical fields are a preferred stimulus because of the speed and ease of application to bulk polymers. While a wide range of electrically triggered actuators are developed, and electrically controlled adhesion between gels is demonstrated, modification of bulk mechanical properties via electrical stimuli remains elusive. Polymers with covalently incorporated ionic charge (polyelectrolytes) should be well suited to achieving this goal since the mechanical properties depend on electrostatic interactions and these charges are intrinsically susceptible to electric fields. Molecular dynamics simulations are utilized here to investigate whether electric fields can modulate the mechanical properties of polyelectrolytes and to understand the governing mechanisms. Mechanical property modulation by electric field is found to be sensitive to the charge distribution—charges must be tightly attached to the polymer backbone, and responsivity is greater if a single backbone contains both positive and negative charges. The dominant mechanisms are reorientation and stretching of the polymer chains, which also elongate the ionic clusters to maintain strong electrostatic interactions throughout deformation. Furthermore, these insights are critical for future experimental realization of polymers with electric field regulated mechanical properties.

36 MATERIALS SCIENCE↗