On the application of Marcus-Hush theory to small polaron chemical dynamics in oxides: its relationship to the Holstein model and the importance of lattice-orbital symmetries.

The chemical dynamics of small polaron hopping within oxides is often interpreted through two-site variations on Marcus-Hush theory, while from a physics perspective small polaron hopping is more often approached from Holstein's solid-state formalism. Here we seek to provide a chemically oriented viewpoint, focusing on small polaron hopping in oxides, concerning these two phenomenological frameworks by employing both tight-binding modelling and first-principles calculations. First, within a semiclassical approach the Marcus-Hush relations are overviewed as a two-site reduction of Holstein's model. Within the single-band regime, similarities and differences between Holstein derived small polaron hopping and the Marcus-Hush model are also discussed. In this context the emergence of adiabaticity (or, conversely, diabaticity) is also explored within each framework both analytically and by directly evolving the system wavefunction. Then, through first-principles calculations of select oxides we explore how coupled lattice and orbital symmetries can impact on hopping properties - in a manner that is quite distinct typical chemical applications of Marcus-Hush theory. These results are then related back to the Holstein model to explore the relative applicability of the two frameworks towards interpreting small polaron hopping properties, where it is emphasized that the Holstein model offers an increasingly more appealing physicochemical interpretation of hopping processes as band and/or coupling interactions increase. Overall, this work aims to strengthen the physically oriented exploration of small polarons and their physicochemical properties in the growing oxide chemistry community.

Signal quality assessment of peripheral venous pressure.

Develop a signal quality index (SQI) for the widely available peripheral venous pressure waveform (PVP). We focus on the quality of the cardiac component in PVP. We model PVP by the adaptive non-harmonic model. When the cardiac component in PVP is stronger, the PVP is defined to have a higher quality. This signal quality is quantified by applying the synchrosqueezing transform to decompose the cardiac component out of PVP, and the SQI is defined as a value between 0 and 1. A database collected during the lower body negative pressure experiment is utilized to validate the developed SQI. All signals are labeled into categories of low and high qualities by experts. A support vector machine (SVM) learning model is trained for practical purpose. The developed signal quality index coincide with human experts' labels with the area under the curve 0.95. In a leave-one-subject-out cross validation (LOSOCV), the SQI achieves accuracy 0.89 and F1 0.88, which is consistently higher than other commonly used signal qualities, including entropy, power and mean venous pressure. The trained SVM model trained with SQI, entropy, power and mean venous pressure could achieve an accuracy 0.92 and F1 0.91 under LOSOCV. An exterior validation of SQI achieves accuracy 0.87 and F1 0.92; an exterior validation of the SVM model achieves accuracy 0.95 and F1 0.96. The developed SQI has a convincing potential to help identify high quality PVP segments for further hemodynamic study. This is the first work aiming to quantify the signal quality of the widely applied PVP waveform.

Inaccuracy of pulse oximetry with dark skin pigmentation: clinical implications and need for improvement.

Recent reports highlight potential inaccuracies of pulse oximetry in patients with various degrees of skin pigmentation. We summarise the literature, provide an overview of potential clinical implications, and provide insights into how pulse oximetry could be improved to mitigate against such potential shortcomings.

Improving pulse oximetry accuracy in dark-skinned patients: technical aspects and current regulations.

Recent concerns regarding the clinical accuracy of pulse oximetry in dark-skinned patients, specifically in detecting occult hypoxaemia, have motivated research on this topic and recently reported in this journal. We provide an overview of the technical aspects of the issue, the sources of inaccuracy, and the current regulations and limitations. These insights offer perspectives on how pulse oximetry can be improved to address these potential limitations.

First-principles redox energy estimates under the condition of satisfying the general form of Koopmans' theorem: An atomistic study of aqueous iron.

In this work, we explore the relative accuracy to which a hybrid functional, in the context of density functional theory, may predict redox properties under the constraint of satisfying the general form of Koopmans' theorem. Taking aqueous iron as our model system within the framework of first-principles molecular dynamics, direct comparison between computed single-particle energies and experimental ionization data is assessed by both (1) tuning the degree of hybrid exchange, to satisfy the general form of Koopmans' theorem, and (2) ensuring the application of finite-size corrections. These finite-size corrections are benchmarked through classical molecular dynamics calculations, extended to large atomic ensembles, for which good convergence is obtained in the large supercell limit. Our first-principles findings indicate that while precise quantitative agreement with experimental ionization data cannot always be attained for solvated systems, when satisfying the general form of Koopmans' theorem via hybrid functionals, theoretically robust estimates of single-particle redox energies are most often arrived at by employing a total energy difference approach. That is, when seeking to employ a value of exact exchange that does not satisfy the general form of Koopmans' theorem, but some other physical metric, the single-particle energy estimate that would most closely align with the general form of Koopmans' theorem is obtained from a total energy difference approach. In this respect, these findings provide important guidance for the more general comparison of redox energies computed via hybrid functionals with experimental data.

Computational and infrared spectroscopic investigations of N-substituted carbazoles.

The carbazole moiety is a commonly identified structural motif in the high-molecular-weight components of petroleum, known as asphaltenes. Detailed characterization of carbazoles is important for understanding the structure of asphaltenes and addressing challenges in the areas of heavy oil recovery, transportation, upgrading, and oil spills, arising from asphaltene properties and composition. In this work we study carbazole and the four N-substituted carbazoles 9-methylcarbazole, 9-ethylcarbazole, 9-vinylcarbazole and 9-phenylcarbazole. Experimental far- and mid-infrared spectra of these five carbazoles are measured using transmission and photoacoustic techniques. The molecular structures of the monomers and the respective dimers, optimized at the ωB97X-D/6-311++G(d,p) level of the density functional theory (DFT), are subjected to harmonic vibrational frequency calculations. The effect of changing substituents on the N-H bond, π-π stacking distances, and angles between monomers within the dimers, in addition to intermolecular interactions, is investigated. Noncovalent interaction analysis is employed to highlight the areas of attractive and repulsive interactions in the dimers. Thermochemistry calculations show that the formation of dimers of all carbazoles is spontaneous at 298 K. Comparison of the calculated vibrational spectra of these compounds with experimental spectra indicates that the existence of both monomers and dimers must be invoked to account for the observed bands in the infrared spectra. Excellent correlations between the experimentally-determined and calculated harmonic vibrational energies are obtained, with an experimental-to-calculated scaling factor of 0.95-0.96. These findings highlight the coupled computational-experimental approach for the interpretation of vibrational spectra and are essential for improving the spectroscopic characterization of N-substituted carbazoles.

Ergodic and Nonergodic Dynamics of Oxygen Vacancy Migration at the Nanoscale in Inorganic Perovskites.

Perovskites are widely utilized either as a primary component or as a substrate in which the dynamics of charged oxygen vacancy defects play an important role. Current knowledge regarding the dynamics of vacancy mobility in perovskites is solely based upon volume- and/or time-averaged measurements. This impedes our understanding of the basic physical principles governing defect migration in inorganic materials. Here, we measure the ergodic and nonergodic dynamics of vacancy migration at the relevant spatial and temporal scales using time-resolved atomic force microscopy techniques. Our findings demonstrate that the time constant associated with oxygen vacancy migration is a local property and can change drastically on short length and time scales, such that nonergodic states lead to a dramatic increase in the migration barrier. This correlated spatial and temporal variation in oxygen vacancy dynamics can extend hundreds of nanometers across the surface in inorganic perovskites.

Modeling and multiobjective optimization of indoor airborne disease transmission risk and associated energy consumption for building HVAC systems.

The COVID-19 pandemic has renewed interest in assessing how the operation of HVAC systems influences the risk of airborne disease transmission in buildings. Various processes, such as ventilation and filtration, have been shown to reduce the probability of disease spread by removing or deactivating exhaled aerosols that potentially contain infectious material. However, such qualitative recommendations fail to specify how much of these or other disinfection techniques are needed to achieve acceptable risk levels in a particular space. An additional complication is that application of these techniques inevitably increases energy costs, the magnitude of which can vary significantly based on local weather. Moreover, the operational flexibility available to the HVAC system may be inherently limited by equipment capacities and occupant comfort requirements. Given this knowledge gap, we propose a set of dynamical models that can be used to estimate airborne transmission risk and energy consumption for building HVAC systems based on controller setpoints and a forecast of weather conditions. By combining physics-based material balances with phenomenological models of the HVAC control system, it is possible to predict time-varying airflows and other HVAC variables, which are then used to calculate key metrics. Through a variety of examples involving real and simulated commercial buildings, we show that our models can be used for monitoring purposes by applying them directly to transient building data as operated, or they may be embedded within a multi-objective optimization framework to evaluate the tradeoff between infection risk and energy consumption. By combining these applications, building managers can determine which spaces are in need of infection risk reduction and how to provide that reduction at the lowest energy cost. The key finding is that both the baseline infection risk and the most energy-efficient disinfection strategy can vary significantly from space to space and depend sensitively on the weather, thus underscoring the importance of the quantitative predictions provided by the models.

Infrared spectra of micro-structured samples with microPhotoacoustic spectroscopy and synchrotron radiation.

Photoacoustic spectroscopy (PAS) measures the photon absorption spectrum of a sample through detection of the acoustic wave generated by the photothermal effect as one modulates the intensity of the incident radiation at each wavelength. We have recently demonstrated the implementation of PAS in a microscopy configuration with mid-infrared radiation (microPAS). In the present work, we describe the performance of microPAS using synchrotron radiation (SR) in diffraction-limited spectromicroscopy and imaging experiments. Spectra were obtained for polystyrene beads, polypropylene fibres, and single fibres of human hair. SR produced microPAS spectra of much higher intensity as compared with those obtained using conventional mid- and near-infrared sources. For hair samples, the penetration depth of mid-infrared light, even with bright SR, is significantly shorter than the probed sample thickness at very low modulation frequencies resulting in saturated PAS spectra. In contrast, microPAS spectra of polymer beads were in general of much better quality than those obtained with conventional sources. We also demonstrated the capability to collect line profiles and line spectra at diffraction limited spatial resolution. The microPAS spectra of beads appear free from appreciable bandshape distortions arising from the real part of the refractive index of the sample. This observation confirms microPAS as an absorption-only technique and establishes it as a valuable new tool in the microspectroscopic analysis of particulates and of samples with a complex topography.

Interpreting interfacial semiconductor-liquid capacitive characteristics impacted by surface states: a theoretical and experimental study of CuGaS2.

Semiconductor-liquid interfaces are essential to the operation of many energy devices. Crucially, the operational characteristics of such devices are dependent upon both the flat band potential and doping concentration present in their solid-state semiconducting region. Traditionally, capacitive "linear" Mott-Schottky plots have often been utilized to extract these two parameters. However, significant concentrations of surface states within semiconductor-liquid junctions can give rise to strong non-linearities that prevent an effective linearity-based analysis. In this work, we detail a theoretical approach for estimating both the doping concentration and flat band potential from the capacitive characteristics of semiconductor-liquid junctions heavily impacted upon by surface states. Our theoretical approach is applied to CuGaS2 immersed in an aqueous electrolyte, for which excellent convergent values of the doping concentration and flat band potential are obtained across a wide range of impedance measurement frequencies. The results suggest a marked improvement over a linearity-based approach that could assist the analysis of many types of semiconductor-liquid junctions subject to high concentrations of surface states.

Fully Quantized Electron Transfer Observed in a Single Redox Molecule at a Metal Interface.

Long-range electron transfer is a ubiquitous process that plays an important role in electrochemistry, biochemistry, organic electronics, and single molecule electronics. Fundamentally, quantum mechanical processes, at their core, manifest through both electron tunneling and the associated transition between quantized nuclear vibronic states (intramolecular vibrational relaxation) mediated by electron-nuclear coupling. Here, we report on measurements of long-range electron transfer at the interface between a single ferrocene molecule and a gold substrate separated by a hexadecanethiol quantum tunneling barrier. These redox measurements exhibit quantized nuclear transitions mediated by electron-nuclear coupling at 4.7 K in vacuum. By detecting the electric force associated with redox events by atomic force microscopy (AFM), with increasing AFM oscillation amplitude, the intensity of the observed  cantilever resonance frequency shift peak increases and then exhibits a series of discrete steps that are indicative of quantized nuclear transitions. The observed peak shapes agree well with a single-electron tunneling model with quantized nuclear state transitions associated with the conversion of the molecule between oxidized and reduced electronic states. This technique opens the door to simultaneously investigating quantized electron and nuclear dynamics in a diverse range of systems.

Electrical Stressing Induced Monolayer Vacancy Island Growth on TiSe2.

To ensure practical applications of atomically thin transition metal dichalcogenides, it is essential to characterize their structural stability under external stimuli such as electric fields and currents. Using vacancy monolayer islands on TiSe2 surfaces as a model system, we have observed nonlinear area evolution and growth from triangular to hexagonal driven by scanning tunneling microscopy (STM) subjected electrical stressing. The observed growth dynamics represent a 2D departure from the linear area growth law expected for bulk vacancy clustering. Our simulations of monolayer island evolution using phase-field modeling and first-principles calculations are in good agreement with our experimental observations, and point toward preferential edge atom dissociation under STM scanning driving the observed nonlinear area growth. We further quantified a parabolic growth rate dependence with respect to the tunneling current magnitude. The results could be potentially important for device reliability in systems containing ultrathin transition metal dichalcogenides and related 2D materials subject to electrical stressing.

Relating Franck-Condon blockade to redox chemistry in the single-particle picture.

In this work, we explore Franck-Condon blockade in the "redox limit," where nuclear relaxation processes occur much faster than the rate of electron transfer. To this end, the quantized rate expressions for electron transfer are recast in terms of a quantized redox density of states (DOS) within a single phonon mode model. In the high temperature regime, this single-particle picture formulation of electron transfer is shown to agree well with the semi-classical rate and DOS expressions developed by Gerischer and Hopfield. Upon incorporation into a two electrode formulation, utilizing the master equation approach, the low temperature quantized conductance features of Franck-Condon blockade are reproduced. Moreover, at sufficiently large reorganization energies, it is argued that Franck-Condon blockade should also be observable in room temperature systems. In general, this work aims to further bridge descriptions of electron transfer and transport in the single-particle picture.

Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy.

One of the main challenges in improving fast charging lithium-ion batteries is the development of suitable active materials for cathodes and anodes. Many materials suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques are able to spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique to measure local ionic transport on LiFePO4 to correlate with the structural and compositional analysis of the same region. By comparing the measured values with density functional theory (DFT) calculations, we demonstrate that Coulomb interactions between ions give rise to a collective activation energy for ionic transport that is dominated by large phase boundary hopping barriers. We successfully measure both the collective activation energy and the smaller single-ion bulk hopping barrier and obtain excellent agreement with values obtained from our DFT calculations.

Step-scan differential Fourier transform infrared photoacoustic spectroscopy (DFTIR-PAS): a spectral deconvolution method for weak absorber detection in the presence of strongly overlapping background absorptions.

The determination of small absorption coefficients of trace gases in the atmosphere constitutes a challenge for analytical air contaminant measurements, especially in the presence of strongly absorbing backgrounds. A step-scan differential Fourier transform infrared photoacoustic spectroscopy (DFTIR-PAS) method was developed to suppress the coherent external noise and spurious photoacoustic (PA) signals caused by strongly absorbing backgrounds. The infrared absorption spectra of acetylene (C2H2) and local air were used to verify the performance of the step-scan DFTIR-PAS method. A linear amplitude response to C2H2 concentrations from 100 to 5000 ppmv was observed, leading to a theoretical detection limit of 5 ppmv. The differential mode was capable of eliminating the coherent noise and dominant background gas signals, thereby revealing the presence of the otherwise hidden C2H2 weak absorption. Thus, the step-scan DFTIR-PAS modality was demonstrated to be an effective approach for monitoring weakly absorbing gases with absorption bands overlapped by strongly absorbing background species.

Electron transfer from the perspective of electron transmission: Biased non-adiabatic intermolecular reactions in the single-particle picture.

In this work, we revisit Hopfield's formulation of non-adiabatic electron transfer between uncorrelated redox species within the single-particle picture description of electron transmission commonly applied in solid-state systems. The formulation is applied to a model system, similar to that often found in solid-state electron tunneling studies, consisting of redox species separated by an insulating tunneling barrier. Redox tunneling across such an insulator is predicted to demonstrate a marked asymmetry, ranging from one to three orders of magnitude between forward and reverse bias electron transfer rates, when reactants possess dissimilar reorganization energies. This significant asymmetry is shown to arise from trapezoidal reshaping of the integrated Gamow tunneling barrier and corresponding transmission probability under an applied bias. In general, this work aims to further bridge concepts between the electron transfer and transport communities.

Interfacial Screening in Ultrafast Voltammetry: A Theoretical Study of Redox-Active Monolayers.

The impact of interfacial screening on electron transfer (ET) at ultrashort time scales is theoretically investigated on redox active monolayers by linear sweep voltammetry (LSV). The charging current associated with the nanosecond screening process is an important experimental determinant in finding both the reorganization energy (λ) and electronic coupling (|M|) through ultrafast methods. On the one hand, time dependent decay of the charging current mitigates its impact on the current contribution from faradaic processes, while on the other hand, allowing substantial decay translates into a reduced upper-bound of applicable scan rates, which are crucial for ultrafast characterization. Analysis of the decay in the charging current suggests that the desired screening may be achieved for relatively weakly coupled systems within the charging time constant. For weakly coupled systems, the scan rate corresponding to nanoscale charging time constants appears to be suitable for the ultrafast investigation of ET characteristics. Moreover, the level of screening achieved at nanosecond decay times is shown to change with the coverage of electrode surface by monolayers; which appears to be accompanied by sharp drops in the time constant during successive saturation of interfacial layers by supporting ions (SI). These observations are expected to help design electrochemical device systems with interfaces capable of high faradaic efficiency at ultrafast limits.

Phase-Field-Crystal Model for Electromigration in Metal Interconnects.

We propose an atomistic model of electromigration (EM) in metals based on a recently developed phase-field-crystal (PFC) technique. By coupling the PFC model's atomic density field with an applied electric field through the EM effective charge parameter, EM is successfully captured on diffusive time scales. Our framework reproduces the well-established EM phenomena known as Black's equation and the Blech effect, and also naturally captures commonly observed phenomena such as void nucleation and migration in bulk crystals. A resistivity dipole field arising from electron scattering on void surfaces is shown to contribute significantly to void migration velocity. With an intrinsic time scale set by atomic diffusion rather than atomic oscillations or hopping events, as in conventional atomistic methods, our theoretical approach makes it possible to investigate EM-induced circuit failure at atomic spatial resolution and experimentally relevant time scales.

Synchronous telehealth for outpatient allergy consultations: A 2-year regional experience.

BACKGROUND: Telehealth continues to advance as a health care modality; however, reported experience for synchronous TeleAllergy is limited. OBJECTIVE: To determine the percentage of new and follow-up visits conducted via TeleAllergy in a hospital-based clinic. METHODS: A retrospective study evaluating the first 2 years of a synchronous patient-to-allergist TeleAllergy platform. RESULTS: A total of 112 synchronous TeleAllergy encounters were conducted from January 2014 through December 2015; 66 (59%) of these were new consultations. The mean (SD) age was 26.9 (15.3) years, and 54% of the participants were female. Food allergy (30%), allergic rhinitis (20%), and urticaria (16%) represented the top 3 consultation reasons. Sixteen of 66 patients (24.2%) and 3 of 46 patients (6.5%) attending new and follow-up TeleAllergy visits, respectively, were recommended for an in-person appointment (P = .02). No difference was found between new and follow-up TeleAllergy visits regarding subsequent telephone communication (41% vs 26%, P = .11) or prescriptions ordered (50% vs 33%, P = .08). New TeleAllergy visits were more likely to have more than 1 laboratory test ordered (45% vs 17%, P = .002). On the basis of patient location, the 112 TeleAllergy visits resulted in an estimated savings of 200 workdays or schooldays, US$58,000 in travel-related costs, and 80,000 kilometers not driven. CONCLUSION: Both new and follow-up visits to the allergist/immunologist were well received by patients and demonstrated significant indirect cost savings, with less than one fourth of the patients recommended for an in-person visit. This appears to be the first systematic assessment of TeleAllergy for new and follow-up patient encounters in a clinic-based allergy/immunology practice.

The role of relative rate constants in determining surface state phenomena at semiconductor-liquid interfaces.

In this work, we present a theoretical study of surface state occupation statistics at semiconductor-liquid interfaces, as it pertains to the evolution of H2 and O2 through water splitting. Our approach combines semiclassical charge transport and electrostatics at the semiconductor-liquid junction, with a master rate equation describing surface state mediated electron/hole transfer. As a model system we have studied the TiO2-water junction in the absence of illumination, where it is shown that surface states might not always equilibrate with the semiconductor. Non-trivial electrostatics, for example including a shifting of the Mott-Schottky plateau in capacitive measurements, are explored when deep-level surface states partially equilibrate with the liquid. We also endeavor to explain observations of non-linearity present in Mott-Schottky plots, as they pertain to surface state occupation statistics. In general, it is intended that the results of this work will serve to further the use and development of quantitative device modeling techniques in the description of H2 evolution at semiconductor-liquid junctions.