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A solid–gas reaction rate modeling framework is applied to characterize degradation in thermochemical materials induced by thermal cycling. Time constants and a kinetic conversion ratio are established for a representative carbonation-calcination reaction, which provides insight into degradation mechanisms and reveals a mitigation strategy by tuning reaction duration.
Non-equilibrium interactions between plasmonic metals and adsorbed molecules lie at the heart of emerging applications such as plasmonic photocatalysis and sensing, though the ultrafast charge and energy transfer mechanisms arising from these interactions are not well understood. Herein, we investigate the ultrafast dynamics of Au nano-islands tethered with a self-assembled monolayer (SAM) of electron-withdrawing 4-mercaptobenzoic acid (4MBA) molecules. Ultrafast UV-visible transient absorption spectroscopy following excitation of the interband transition in Au reveals three well-known, characteristic time constants that quantify electron–electron (el–el), electron–phonon (el–ph) and phonon–phonon (ph–ph) scattering lifetimes. When comparing the dynamics of bare Au and 4MBA-Au, we find that the el–ph and ph–ph scattering lifetimes are notably longer in 4MBA-Au. Density functional perturbation theory calculations ascribe the elongation in el–ph lifetimes in 4MBA-Au to the significant coupling of acoustic phonon modes of Au with certain molecular vibrations of 4MBA, leading to decreased spatial overlap between carrier electronic states and the acoustic modes. We speculate that the elongation of ph–ph scattering lifetimes in 4MBA-Au arises due to poor thermal conductivity of the SAM which disrupts efficient energy dissipation from Au to the environment, thus slowing down the thermalization of phonons. This work provides a glimpse into how molecular adsorbates modify the charge carrier and phonon dynamics of Au and sets the stage for further systematic exploration of plasmonic metal–molecule interactions.
Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.
Thermal neutron detectors based on hexagonal boron nitride ( h -BN) epilayers have demonstrated a record high efficiency among solid-state detectors at 58%. It was found that the performance of h -BN detectors is profoundly influenced by charge recombination at the surfaces. The dynamic process of surface oxidation in h -BN epilayers has been probed by x-ray photoelectron spectroscopy. The spectra of high-resolution (0.1 eV) scans indicated that the linewidth of the B 1s peak at 190.6 eV increased and the peak intensity decreased with an increase in exposure time in-air (t air ). The main B 1s peak at 190.6 eV evolved into multiple peaks at a higher binding energy position due to oxygen impurities tending to occupy nitrogen sites and form the B–O bond. Time constants of the oxidation process have been determined, revealing that the formation process of the B–O bond is very fast and within minutes in h -BN. The results suggest that reducing nitrogen vacancy generation during growth and employing surface treatment techniques would further improve the performance of h -BN devices.
Photoactive yellow protein (PYP) is a signaling protein whose internal p-coumaric acid chromophore undergoes reversible, light-induced trans-to-cis isomerization, which triggers a sequence of structural changes that ultimately lead to a signaling state. Since its discovery nearly 40 years ago, PYP has attracted much interest and has become one of the most extensively studied proteins found in nature. The method of time-resolved crystallography, pioneered by Keith Moffat, has successfully characterized intermediates in the PYP photocycle at near atomic resolution over 12 decades of time down to the sub-picosecond time scale, allowing one to stitch together a movie and literally watch a protein as it functions. But how close to reality is this movie? To address this question, results from numerous complementary time-resolved techniques including x-ray crystallography, x-ray scattering, and spectroscopy are discussed. Emerging from spectroscopic studies is a general consensus that three time constants are required to model the excited state relaxation, with a highly strained ground-state cis intermediate formed in less than 2.4 ps. Persistent strain drives the sequence of structural transitions that ultimately produce the signaling state. Crystal packing forces produce a restoring force that slows somewhat the rates of interconversion between the intermediates. Moreover, the solvent composition surrounding PYP can influence the number and structures of intermediates as well as the rates at which they interconvert. When chloride is present, the PYP photocycle in a crystal closely tracks that in solution, which suggests the epic movie of the PYP photocycle is indeed based in reality.
Thermal Kinetic-Inductance Detectors (TKIDs) combine the excellent noise performance of traditional bolometers with a radio frequency multiplexing architecture that enables the large detector counts needed for the next generation of millimeter-wave instruments. In this paper, we first discuss the expected noise sources in TKIDs and derive the limits where the phonon noise contribution dominates over the other detector noise terms: generation–recombination, amplifier, and two-level system noise. Second, we characterize aluminum TKIDs in a dark environment. We present measurements of TKID resonators with quality factors of about 10 5 at 80 mK. We also discuss the bolometer thermal conductance, heat capacity, and time constants. These were measured by the use of a resistor on the thermal island to excite the bolometers. These dark aluminum TKIDs demonstrate a noise equivalent power, NEP = 2 × 10 − 17 W / Hz , with a 1 / f knee at 0.1 Hz, which provides background noise limited performance for ground-based telescopes observing at 150 GHz.
Reduced scale wind turbines can be extremely cost-effective to test new rotor concepts since prototype costs are heavily dependent on the rotor diameter. Ideally, the scaled model would have the same non-dimensional deflections, dynamics, and control behavior as the full-scale model. This would provide a high-fidelity demonstration of the full-scale performance, which is ideal if the full-scale turbine has significant aeroelastic interactions. To this end, servo-aero-gravo-elastic (SAGE) scaling is developed and applied to a 13-MW turbine that is scaled to a 20% scale model. The scaling preserves the tip-speed ratio, the rotor speed normalized by the flapping frequency, and the tip deflections normalized by the blade length. In addition, the controller employs the same control structure (gain-scheduled pitch control and variable speed torque control) and is scaled dynamically (e.g., matching non-dimensional time constant of the pitch angle, etc.). Furthermore, the thrust, gravity, and centrifugal moments are scaled such that the load angles are preserved as a function of a non-dimensional wind speed. However, the environmental scaling must consider differences in Reynolds number (since this parameter cannot be held constant) and subsequent changes in the axial induction factor. While the presented results showcase these differences during operational conditions, the non-dimensional tip deflections remain comparable through all wind speed ranges, indicating the viability of the SAGE scaling method in matching full-scale aeroelastic responses.
It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).
The electrical and structural characteristics of 50-nm-thick zinc oxide (ZnO) metal-semiconductor-metal ultraviolet (UV) photodetectors subjected to proton irradiation at different temperatures are reported and compared. The devices were irradiated with 200 keV protons to a fluence of 1016 cm−2. Examination of the x-ray diffraction (XRD) rocking curves indicates a preferred (100) orientation prior to irradiation, with decrease in crystal quality afterward. Additionally, peak shifts in XRD and Raman spectra of the control sample relative to well-known theoretical positions are indicative of tensile strain in the as-deposited ZnO films. Shifts toward theoretical unstrained positions are observed in the irradiated films, which indicates partial relaxation. Raman spectra also indicate increase in oxygen vacancies (VO) and zinc interstitial defects (Zni) compared to the control sample. Additionally, transient photocurrent measurements performed on each sample at different temperatures showed up to 2× increase in photocurrent decay time constants for irradiated samples vs the control. This persistent photoconductive behavior is linked to the activation of electron and hole traps near the surface, and to the desorption and reabsorption of O2 molecules on the ZnO surface under the influence of UV light. Using an Arrhenius model, trap activation energies were extracted and, by comparing with known energies from the literature, the dominant defects contributing to persistent photoconductivity for each irradiation condition were identified. The persistence of differences in photocurrent transients between different samples months after irradiation indicates that the defects introduced by the suppression of thermally activated dynamic annealing processes have a long-term deleterious effect on device performance.
In this paper, we present the physics and design-space exploration of a novel pulse compression photoconductive switch (PCPS) using semi-insulating gallium arsenide (GaAs) operating in the negative differential mobility (NDM) regime of electron transport. We systematically quantify the relationship between the PCPS performance and various design options, including contact separation, laser energy and placement, and trap dynamics. Specifically, we report the full-width at half-maximum and the peak output current generated by the PCPS as a function of applied electrical and optical bias. We discuss the optimal spacing between the electrodes and the distance of the laser spot to the anode to achieve higher electron confinement and superior radio-frequency (RF) metrics. Reducing the laser energy is important to prevent the appearance of secondary peaks due to diffusive transport, but there exists a trade-off between the bandwidth and the maximum current of the PCPS. We also compare the PCPS response with and without trap dynamics and find that the electrostatic screening from the trap-induced space charge is time-independent when the trapping time constant is set larger than the recombination lifetime. Overall, trap dynamics are detrimental to performance, unless the compensation doping scheme to achieve semi-insulating GaAs is carefully selected. Results presented in this paper can be used by experimentalists to fine-tune the PCPS design parameters to meet the specifications of various RF applications. Moreover, our results will provide a strong theoretical basis to the measurements of PCPS devices using GaAs and other NDM materials under investigation.
Solid-state nuclear magnetic resonance can be enhanced using unpaired electron spins with a method known as dynamic nuclear polarization (DNP). Fundamentally, DNP involves ensembles of thousands of spins, a scale that is difficult to match computationally. This scale prevents us from gaining a complete understanding of the spin dynamics and applying simulations to design sample formulations. We recently developed an ab initio model capable of calculating DNP enhancements in systems of up to ~1000 nuclei; however, this scale is insufficient to accurately simulate the dependence of DNP enhancements on radical concentration or magic angle spinning (MAS) frequency. We build on this work by using ab initio simulations to train a hybrid model that makes use of a rate matrix to treat nuclear spin diffusion. We show that this model can reproduce the MAS rate and concentration dependence of DNP enhancements and build-up time constants. Finally, we then apply it to predict the DNP enhancements in core–shell metal-organic-framework nanoparticles and reveal new insights into the composition of the particles’ shells.
Here we present a sub-picosecond resolved investigation of the structural solvent reorganization and geminate recombination dynamics following 400 nm two-photon excitation and photodetachment of a valence p electron from the aqueous atomic solute, I–(aq). The measurements utilized time-resolved X-ray Absorption Near Edge Structure (TR-XANES) spectroscopy and X-ray Solution Scattering (TR-XSS) at the Linac Coherent Light Source x-ray free electron laser in a laser pump/x-ray probe experiment. The XANES measurements around the L 1 -edge of the generated nascent iodine atoms (I 0 ) yield an average electron ejection distance from the iodine parent of 7.4 ± 1.5 Å with an excitation yield of about 1/3 of the 0.1M NaI aqueous solution. The kinetic traces of the XANES measurement are in agreement with a purely diffusion-driven geminate iodine–electron recombination model without the need for a long-lived (I 0 :e–) contact pair. Nonequilibrium classical molecular dynamics simulations indicate a delayed response of the caging H 2 O solvent shell and this is supported by the structural analysis of the XSS data: We identify a two-step process exhibiting a 0.1 ps delayed solvent shell reorganization time within the tight H-bond network and a 0.3 ps time constant for the mean iodine–oxygen distance changes. The results indicate that most of the reorganization can be explained classically by a transition from a hydrophilic cavity with a well-ordered first solvation shell (hydrogens pointing toward I–) to an expanded cavity around I 0 with a more random orientation of the H 2 O molecules in a broadened first solvation shell.
Vanadium oxide films are widely employed as thermal detectors in uncooled infrared detection systems due to their high temperature coefficient of resistance near room temperature. One strategy toward maximizing detectivity and reducing the thermal time constant in these systems is to minimize the system platform dimensions. This approach necessitates thinner film thicknesses ([Formula: see text]100 nm), for which there is little information regarding thermal sensing performance. Herein, we report on the sensitivity of reactively sputtered vanadium oxide thin film resistive thermometers nominally ranging from 100 to 25 nm and assess the influence of thermal annealing. Here we demonstrate that films in this minimum limit of thickness maintain a high temperature coefficient while additionally providing an enhancement in characteristics of the noise equivalent power.
Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, in this paper, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au 20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au 20 beyond the Born–Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au 20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au 20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ~10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.
We have built and commissioned a compact in situ 3He polarizer based on spin-exchange optical pumping for the engineering materials diffractometer, named VULCAN, at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory. The system achieved 78% 3He polarization with a short pump-up time constant of 2.2 h. Its first deployment in an in situ half-polarized neutron diffraction experiment on a magnetic shape memory alloy, Ni–Mn–Ga, revealed changes in magnetization coupled to deformation twinning under compression. With this new capability, VULCAN has become the first diffractometer at SNS capable of performing polarized neutron experiments, opening new opportunities to study a wider range of magnetism-related material behaviors under varied thermal, mechanical, electrical, and/or magnetic fields.
Intramolecular charge transfer and the associated changes in molecular structure in N,N'-dimethylpiperazine are tracked using femtosecond gas-phase X-ray scattering. The molecules are optically excited to the 3p state at 200 nm. Following rapid relaxation to the 3s state, distinct charge-localized and charge-delocalized species related by charge transfer are observed. The experiment determines the molecular structure of the two species, with the redistribution of electron density accounted for by a scattering correction factor. The initially dominant charge-localized state has a weakened carbon–carbon bond and reorients one methyl group compared with the ground state. Subsequent charge transfer to the charge-delocalized state elongates the carbon–carbon bond further, creating an extended 1.634 Å bond, and also reorients the second methyl group. At the same time, the bond lengths between the nitrogen and the ring-carbon atoms contract from an average of 1.505 to 1.465 Å. The experiment determines the overall charge transfer time constant for approaching the equilibrium between charge-localized and charge-delocalized species to 3.0 ps.
An ongoing effort looking at bioblendstocks to function as drop-in replacements or blending components for gasoline has identified a large number of candidate fuels. This work documents an approach for rapid screening of candidate fuels using relatively small sample sizes ($\mathcal{O}(\mu\,{\rm l})$) that targets two key physical properties of liquid fuels—surface tension and viscosity. The approach utilizes shape oscillation dynamics of single droplets generated by a piezo-electric device and their decay over time. Strobed imaging of the oscillation process is used along with image processing, edge detection, and data analysis to capture the decay of the oscillation over time. The time constant of the decay process along with oscillation frequency are then used to estimate viscosity and surface tension using a theory for small amplitude droplet oscillations. Measurements are obtained for primary reference fuels (isooctane and n-heptane) as well as candidate fuels from four bio-derived functional groups of interest. Measurement results for surface tension and viscosity are correlated with literature data as well as measurements from standard reference instruments. The measurement results show that the droplet oscillation based approach is capable of reproducing surface tension and viscosity values for the tested fuels within deviations of 7% and 13% respectively from literature data. Results are obtained using an average of 5 µl per fuel within about 20 s, thus demonstrating a small-volume, high-throughput approach that can be used for screening of candidate bioblendstock fuels.
One of the challenges of electron density measurements of an atmospheric pressure plasma (APP) with a laser interferometer is the significant and unwanted phase shift caused by changes in the neutral gas density. These unwanted phase shifts can be mitigated and plasma density measured using an interferometer architecture called a dispersion interferometer (DI). A DI is composed of two nonlinear orientation patterned GaAs crystals for frequency doubling and measures the phase shift induced by a plasma in the interference signal between two second-harmonic beams. Measurement of plasma dynamics or a short plasma pulse in less than a millisecond is enabled with heterodyne detection in a DI using an acousto-optic cell with a frequency of 40 MHz. This heterodyne DI (HDI) is targeted to measure APPs in an electron density range of 10 20 –10 24 m −3 . Finally, the HDI achieves a line-integrated density resolution of 2 × 10 15 m −2 (a phase resolution of 0.005°) with a time constant of 1 μs using ensemble averaging techniques.