Daniel Slaughter

Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface

Understanding interfacial charge-transfer processes on the atomic level is crucial to support the rational design of energy-challenge relevant systems such as solar cells, batteries, and photocatalysts. A femtosecond time-resolved core-level photoelectron spectroscopy study is performed that probes the electronic structure of the interface between ruthenium-based N3 dye molecules and ZnO nanocrystals within the first picosecond after photoexcitation and from the unique perspective of the Ru reporter atom at the center of the dye. A transient chemical shift of the Ru 3d inner-shell photolines by (2.3 ± 0.2) eV to higher binding energies is observed 500 fs after photoexcitation of the dye. The experimental results are interpreted with the aid of ab initio calculations using constrained density functional theory. Strong indications for the formation of an interfacial charge-transfer state are presented, providing direct insight into a transient electronic configuration that may limit the efficiency of photoinduced free charge-carrier generation.

Forward angle scattering effects in the measurement of total cross sections for positron scattering

Measurements of total scattering by positron impact have typically excluded a significant portion of the forward scattering angles of the differential cross section. This paper demonstrates the effect that this can have on measurements of the total cross section. We show that much of the apparent disagreement between experimental measurements of positron scattering from atoms and molecules may be explained by this excluded angular range. It is shown that this same effect may also lead to an anomalous energy dependence of some cross sections.

Total and positronium formation cross sections for positron scattering from H2O and HCOOH

Total and positronium formation cross sections have been measured for positron scattering from H2O and HCOOH using a positron beam with an energy resolution of 60 meV (full-width at half-maximum (FWHM)). The energy range covered is 0.5–60 eV, including an investigation of the behavior of the onset of the positronium formation channel using measurements with a 50 meV energy step, the result of which shows no evidence of any channel coupling effects or scattering resonances for either molecule.

Low-energy positron interactions with xenon

Low-energy interactions of positrons with xenon have been studied both experimentally and theoretically. The experimental measurements were carried out using a trap-based positron beam with an energy resolution of ?80?meV, while the theoretical calculations were carried out using the convergent close-coupling method and the relativistic optical potential approach. Absolute values of the grand total, positronium formation and grand total minus positronium formation cross sections are presented over the energy range of 1?60?eV. Elastic differential cross sections (DCS), for selected energies, are also presented both below and above the positronium formation threshold. Fine energy-step measurements of the positronium formation cross section over the energy range of 4.4?8.4?eV, and measurements of the elastic DCS at the energies of 5.33 and 6.64?eV, have been carried out to investigate the ionization threshold regions corresponding to the 2P3/2 and 2P1/2 states of the Xe+ ion. The present results are compared with both experimental and theoretical values from the literature where available.

Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources

An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with the retarding ratio can be well approximated by applying Liouvilles theorem of constant emittance to the electron trajectories inside the lens system. The performance of the setup is demonstrated by characterizing the laser fluence-dependent transient surface photovoltage response of a laser-excited Si(100) sample.

Dissociative electron attachment to carbon dioxide via the 8.2 eV Feshbach resonance

Momentum imaging experiments on dissociative electron attachment (DEA) to CO2 are combined with the results of ab initio calculations to provide a detailed and consistent picture of the dissociation dynamics through the 8.2 eV resonance, which is the major channel for DEA in CO2. The present study resolves several puzzling misconceptions about this system.

Dynamics of the Dissociating Uracil Anion Following Resonant Electron Attachment

We report a combined experimental and theoretical investigation of dissociative electron attachment (DEA) to the nucleobase uracil. Using ion momentum imaging experiments employing a DEA reaction microscope we have measured 3-dimensional momentum distributions of specific anionic fragments following DEA to uracil by 6 eV electrons. From the measured anion fragment kinetic energy we determine the possible dissociation pathways and the total kinetic energy release. We employ electronic structure and electron scattering calculations to determine the probability for electron attachment in the molecular frame. Combining these calculations with the imaging measurements, we reveal several key features of the coupled electronic and nuclear dynamics of DEA.

A momentum imaging microscope for dissociative electron attachment

We describe an experimental approach to image the three-dimensional (3D) momentum distribution of the negative ions arising from dissociative electron attachment (DEA). The experimental apparatus employs a low energy pulsed electron gun, an effusive gas source and a 4π solid-angle ion momentum imaging spectrometer consisting of a pulsed ion extraction field, an electrostatic lens, and a time- and position-sensitive detector. The time-of-flight and impact position of each negative ion are measured event by event in order to image the full 3D ion momentum sphere. The system performance is tested by measuring the anion momentum distributions from two DEA resonances, namely H(-) from H(2)O(-) ((2)B(1)) and O(-) from O(2)(-) ((2)Π(u)). The results are compared with existing experimental and theoretical data.

Dissociative electron attachment to carbon dioxide via the 2

Author(s): Moradmand, A; Slaughter, DS; Haxton, DJ; Rescigno, TN; McCurdy, CW; Weber, T; Matsika, S; Landers, AL; Belkacem, A; Fogle, M | Abstract: Momentum imaging measurements from two experiments are presented and interpreted with the aid of ab initio theoretical calculations to describe the dissociative electron attachment (DEA) dynamics of CO2. The dynamics of the transient negative ions of CO2- involve several conical intersections taking part in mechanisms that have only recently been understood. We address the problem of how the 4-eV 2Πu shape resonance in CO2 proceeds to dissociate to CO(1Σ+) + O-(2P) by DEA.

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Positron impact ionization of helium is studied with fully resolved momentum vectors of all continuum particles. An imaging multi-particle momentum spectrometer (reaction microscope) detecting all final state particles over the full solid angle was applied. This apparatus was connected to the NEPOMUC facility delivering intense positron beams tuneable over a large energy range with good beam quality. At 80 eV impact energy about 5000 triple coincidence events were collected. Cross sections as function of the longitudinal particle momentum show strong differences compared to respective electron impact ionization data most likely originating from the reversed post collision interaction in both cases. Calculations using the 3 Coulomb wavefunction method show clear discrepancies from the experimental results.