Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-Ray Spectroscopy.

The electronic excitation occurring on adsorbates at ultrafast timescales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) of a simple well-known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel [Ni(100)] surface, following intense laser optical pumping at 400 nm. We observe ultrafast (∼100  fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate.

Symmetry-resolved CO desorption and oxidation dynamics on O/Ru(0001) probed at the C K-edge by ultrafast x-ray spectroscopy.

We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10 Torr) and O (3 × 10 Torr). Under these conditions, we detect two transient CO species with narrow 2π* peaks, suggesting little 2π* interaction with the surface.

Quantifying and manipulating the angles of light in experimental measurements of plant gas exchange.

Diffuse light has been shown to alter plant leaf photosynthesis, transpiration and water-use efficiency. Despite this, the angular distribution of light for the artificial light sources used with common gas exchange systems is unknown. Here, we quantify the angular distribution of light from common gas exchange systems and demonstrate the use of an integrating sphere for manipulating those light distributions.

Methanol decomposition on Ni(111) and O/Ni(111).

Methanol decomposition on Ni(111) surfaces has been studied in the presence and absence of oxygen using temperature-programmed desorption and temperature-dependent sum frequency generation spectroscopy. Under both conditions the C-H and O-H bonds break, forming carbon monoxide and atomic hydrogen on the surface. No C-O bond scission was observed, limiting the number of reaction pathways.

Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy.

We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime.

Expansion of telehealth in primary care during the COVID-19 pandemic: benefits and barriers.

The novel coronavirus disease 2019 (COVID-19) pandemic remarkably accelerated the adoption of telemedicine in outpatient settings. Out of necessity, virtual care became a preferred and default modality of extending primary care services to health care consumers. Although telemedicine is not a new concept and had been used in many organizations and health systems, the COVID-19 pandemic scaled up its use in a variety of health care settings.

Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy.

The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds.

Impact of Positive and Negative Motivation and Music on Jump Shot Efficiency among NAIA Division I College Basketball Players.

The objective of this study was to determine whether music, positive feedback, and/or negative feedback impacted jump shooting performance in NAIA Division I male and female basketball players. Using a cross-over design, participants (N=20) took 50 shots from 15 feet and 50 shots from the 3-point line under four conditions (silence, music, positive feedback, negative feedback). The number of shots made were recorded and a one-way ANOVA was used to determine differences between gender.

Atom-specific activation in CO oxidation.

We report on atom-specific activation of CO oxidation on Ru(0001) via resonant X-ray excitation. We show that resonant 1 core-level excitation of atomically adsorbed oxygen in the co-adsorbed phase of CO and oxygen directly drives CO oxidation. We separate this direct resonant channel from indirectly driven oxidation via X-ray induced substrate heating.

Real-Time Elucidation of Catalytic Pathways in CO Hydrogenation on Ru.

The direct elucidation of the reaction pathways in heterogeneous catalysis has been challenging due to the short-lived nature of reaction intermediates. Here, we directly measured on ultrafast time scales the initial hydrogenation steps of adsorbed CO on a Ru catalyst surface, which is known as the bottleneck reaction in syngas and CO reforming processes. We initiated the hydrogenation of CO with an ultrafast laser temperature jump and probed transient changes in the electronic structure using real-time X-ray spectroscopy.

Postural Preparation to Stepping: Coupled Center of Pressure Shifts in the Anterior-Posterior and Medio-Lateral Directions.

We explored changes in the postural preparation to stepping introduced by modifications of the initial coordinates of the center of pressure (COP). We hypothesized that the postural adjustments in the anterior-posterior direction would persist across all initial COP manipulations while the adjustments in the medio-lateral direction would be highly sensitive to the initial COP coordinate. Healthy subjects stood on a force plate, shifted the body weight to one of the initial conditions that spanned the range of COP coordinates in both directions, and initiated a single step or started to walk.

Chemical Bond Activation Observed with an X-ray Laser.

The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access.

THz-Pulse-Induced Selective Catalytic CO Oxidation on Ru.

We demonstrate the use of intense, quasi-half-cycle THz pulses, with an associated electric field component comparable to intramolecular electric fields, to direct the reaction coordinate of a chemical reaction by stimulating the nuclear motions of the reactants. Using a strong electric field from a THz pulse generated via coherent transition radiation from an ultrashort electron bunch, we present evidence that CO oxidation on Ru(0001) is selectively induced, while not promoting the thermally induced CO desorption process. The reaction is initiated by the motion of the O atoms on the surface driven by the electric field component of the THz pulse, rather than thermal heating of the surface.

Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations.

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species.

Surface chemistry. Probing the transition state region in catalytic CO oxidation on Ru.

Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS).

Global stress response during a social stress test: impact of alexithymia and its subfactors.

Objectives: Alexithymia is a personality trait characterized by difficulties in identifying, describing and communicating one's own emotions. Recent studies have associated specific effects of this trait and its subfactors with hypothalamo-pituitary-adrenal (HPA) axis markers during stress. The aim of this study was to analyze the association between alexithymia and its subfactors with HPA and sympatho-adrenal medullar (SAM) activity.

Influence of ankle loading on the relationship between temporal pressure and motor coordination during a whole-body paired task.

We investigated whether ankle loading modifies the relationship between temporal pressure and motor coordination during a whole-body paired task. Eight young healthy adults standing in an erect posture performed multiple series of simultaneous rapid leg flexions paired with ipsilateral index finger extensions. They repeated the task ten times in three load conditions: unloaded, loaded (where additional 5-kg inertia was attached to the ankles), and post-loaded (immediately following the loaded condition).

Age-related differences in motor coordination during simultaneous leg flexion and finger extension: influence of temporal pressure.

Although the effect of temporal pressure on spatio-temporal aspects of motor coordination and posture is well established in young adults, there is a clear lack of data on elderly subjects. This work examined the aging-related effects of temporal pressure on movement synchronization and dynamic stability. Sixteen young and eleven elderly subjects performed series of simultaneous rapid leg flexions in an erect posture paired with ipsilateral index-finger extensions, minimizing the difference between heel and finger movement onsets.

Phytoremediation of 1,4-dioxane-containing recovered groundwater.

The results of a pilot-scale phytoremediation study are reported in this paper. Small plots of trees established on a closed municipal waste landfill site were irrigated with recovered groundwater containing 1,4-dioxane (dioxane) and other volatile organic compounds (VOCs). The plots were managed to minimize the leaching of irrigation water, and leaching was quantified by the use of bromide tracer.

Real-time observation of surface bond breaking with an x-ray laser.

We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption.

Influence of temporal pressure on anticipatory postural control of medio-lateral stability during rapid leg flexion.

During leg flexion from erect posture, postural stability along the medio-lateral direction is organized in advance during "anticipatory postural adjustments" (APAs). This study aimed to investigate the influence of temporal pressure on this anticipatory postural control of medio-lateral stability. Eight young healthy participants performed series of leg flexions (1) as soon as possible in response to an acoustic signal (reaction-time condition; condition with temporal pressure) and (2) in a self-initiated condition (no temporal pressure).

Electron kinetic energies from vibrationally promoted surface exoemission: evidence for a vibrational autodetachment mechanism.

We report kinetic energy distributions of exoelectrons produced by collisions of highly vibrationally excited NO molecules with a low work function Cs dosed Au(111) surface. These measurements show that energy dissipation pathways involving nonadiabatic conversion of vibrational energy to electronic energy can result in electronic excitation of more than 3 eV, consistent with the available vibrational energy. We measured the dependence of the electron energy distributions on the translational and vibrational energy of the incident NO and find a clear positive correlation between final electron kinetic energy and initial vibrational excitation and a weak but observable inverse dependence of electron kinetic energy on initial translational energy.

Modulation of anticipatory postural adjustments in the anticipation-coincidence task.

This study was designed to (a) verify whether the time available for movement preparation and execution modulates anticipatory postural adjustments/focal movement coordination and (b) determine to what extent the coordination in an anticipation-coincidence (AC) timing task is specific. Ten subjects performed an arm-raising movement from standing position in the reaction time, self-initiated (SI), and AC conditions. In the latter condition, subjects had to synchronize movement initiation or the end of the movement to the passage of a visual mobile on a target.