Experiences and Lessons Learned From the RADx-UP Consortium Community Engagement Projects.

In this study, we used emerging community engagement frameworks to describe the structure and outcomes of a large-scale, community-engaged, research-to-practice initiative, RADx-UP. Qualitative methods were used to analyze survey and meeting data from 2022 for RADx-UP projects. Most projects had diverse partners, achieved moderate levels of community engagement, and experienced positive outcomes. Challenges related to engagement readiness and partnership functioning. These findings demonstrate that community engagement is measurable and valuable. However, additional support is needed to achieve the highest engagement. (Am J Public Health. 2024;114(S5):S405-S409. https://doi.org/10.2105/AJPH.2024.307615).

Time propagation of electronic wavefunctions using nonorthogonal determinant expansions.

The use of truncated configuration interaction in real-time time-dependent simulations of electron dynamics provides a balance of computational cost and accuracy, while avoiding some of the failures associated with real-time time-dependent density functional theory. However, low-order truncated configuration interaction also has limitations, such as overestimation of polarizability in configuration interaction singles, even when perturbative doubles are included. Increasing the size of the determinant expansion may not be computationally feasible, and so, in this work, we investigate the use of nonorthogonality in the determinant expansion to establish the extent to which higher-order substitutions can be recovered, providing an improved description of electron dynamics. Model systems are investigated to quantify the extent to which different methods accurately reproduce the (hyper)polarizability, including the high-harmonic generation spectrum of H2, water, and butadiene.

Protonation state control of electric field induced molecular switching mechanisms.

Scanning tunneling microscopy tip-induced deprotonation has been demonstrated experimentally and can be used as an additional control mechanism in electric-field induced molecular switching. The goal of the current work is to establish whether (de)protonation can be used to inhibit or enhance the electric field controlled thermal and photoisomerization processes. Dihydroxyazobenzene is used as a model system, where protonation/deprotonation of the free hydroxyl moiety changes the azo bond order, and so modifies the rate of electric field induced isomerization. Through the combined action of deprotonation and applied field, it was found that the cis-to-trans thermal isomerization barrier could be completely removed, changing the isomerization half-life from the order of several months. In addition, due to the presence of multiple isomerization mechanisms, electric fields could modify the isomerization kinetics by increasing the number of energetically viable isomerization pathways, rather than reducing the activation barrier of the lowest energy pathway. Excited state calculations indicated that the protonation state and electric field could be used together to control the presence of electronic degeneracies along the rotation pathway between S0/S1, and along all three pathways between S1/S2. This work provides insight into the mechanisms that enable the use of protonation state, light, and electric fields in concert to control molecular switches.

Reactivity of Group 5 and 6 Single-Site Photocatalysts for Partial Oxidation of Methane: Comparison of Chromium, Niobium, and Tungsten-Doped Mesoporous Amorphous Silica.

Single-site transition-metal-doped photocatalysts can potentially be used for partial oxidation of methane (POM) at remote sites where natural gas is extracted and methane is often flared or released to the atmosphere. While there have been several investigations into the performance of vanadium, there has been no general survey of the performance of other metals. This work aims and examines Cr, Nb, and W metal oxide materials embedded in amorphous SiO2 to determine the viability of each metal in catalyzing the POM. Photoexcited states are examined to determine the nature of the photoactivated species, and then the subsequent POM reaction mechanisms are elucidated. Using the calculated energies of reaction intermediates and transition states, the rate of methanol formation is evaluated through the use of a microkinetic model. The findings indicate that all three metals are potentially more suitable for catalyzing POM than vanadium but that niobium shows the most favorable energy profile.

The Angular Gyrus as a Hub for Modulation of Language-related Cortex by Distinct Prefrontal Executive Control Regions.

It has become clear in recent years that reading, while relying on domain-specific language processing regions, also involves regions that implement executive processes more broadly. Such executive control is generally considered to be implemented by prefrontal regions, which exert control via connectivity that allows them to modulate processing in target brain regions. The present study examined whether three previously identified and distinct executive control regions in the pFC [Wang, K., Banich, M. T., Reineberg, A. E., Leopold, D. R., Willcutt, E. G., Cutting, L. E., et al. Left posterior prefrontal regions support domain-general executive processes needed for both reading and math. Journal of Neuropsychology, 14, 467-495, 2020] show similar patterns of functional connectivity (FC) during a reading comprehension task as compared with a symbol identification condition. Our FC results in a sample of adolescents (n = 120) suggest all three regions commonly show associations with activity in "classic" left hemisphere reading areas, including the angular and supramarginal gyri, yet each exhibits differential connectivity as well. In particular, precentral regions show differential FC to parietal portions of the dorsal language stream, the inferior frontal junction shows differential FC to middle temporal regions of the right hemisphere and other regions involved in semantic processing, and portions of the inferior frontal gyrus show differential FC to an extensive set of right hemisphere prefrontal regions. These results suggest that prefrontal control over language-related regions occurs in a coordinated yet discrete manner.

Role of Exact Exchange in Difference Projected Double-Hybrid Density Functional Theory for Treatment of Local, Charge Transfer, and Rydberg Excitations.

Difference approaches to the study of excited states have undergone a renaissance in recent years, with the development of a plethora of algorithms for locating self-consistent field approximations to excited states. Density functional theory is likely to offer the best balance of cost and accuracy for difference approaches, and yet there has been little investigation of how the parametrization of density functional approximations affects performance. In this work, we aim to explore the role of the global Hartree-Fock exchange parameter in tuning accuracy of different excitation types within the framework of the recently introduced difference projected double-hybrid density functional theory approach and contrast the performance with conventional time-dependent double-hybrid density functional theory. Difference projected double-hybrid density functional theory was demonstrated to give vertical excitation energies with average error and standard deviation with respect to multireference perturbation theory comparable to more expensive linear-response coupled cluster approaches ( J. Chem. Phys.2020, 153, 074103). However, despite benchmarking of local excitations, there has been no investigation of the methods performance for charge transfer or Rydberg excitations. In this work we report a new benchmark of charge transfer, Rydberg, and local excited state vertical excitation energies and examine how the exact Hartree-Fock exchange affects the benchmark performance to provide a deeper understanding of how projection and nonlocal correlation balance differing sources of error in the ground and excited states.

The COVID-19 pandemic: Analysing nursing risk, care and careerscapes.

This qualitative study explores how junior nurses, and some who were still in training, navigated the complexities and uncertainties engendered by the COVID-19 pandemic. Data are drawn from in-depth interviews with 18 students/nurses in Christchurch, New Zealand. Managing intertwining risk, care and careerscapes takes an intensified form as existing infection control rules, established norms of care, boundaries between home and work and expected career trajectories roil. 'Safe' and 'risky' spaces are porous but maintained using contextual, critical, clinical judgement. Carescapes are stretched, both within and beyond the walls of healthcare settings. Within the COVID-19 riskscape, careerscapes are open to both threat and opportunity. Countries demand much of their healthcare staff in times of heath crises, but have a limited appreciation of what it takes to translate seemingly tightly bounded protocols into effective practice. The labour required in this work of translation is navigated moment by moment. To surface some of this invisible work, those implementing pandemic plans may need to more carefully consider how to incorporate attention to the work/home/public boundary as well as overtly acknowledging the invisible emotional, physical and intellectual labour carried out in crisis risk, care and careerscapes.

Oriented External Electric Field Tuning of Unsubstituted Azoheteroarene Thermal Isomerization Half-Lives.

Azoheteroarenes are relatively new photoswitchable compounds, where one of the phenyl rings of an azobenzene molecule is replaced by a heteroaromatic five-membered ring. Recent findings on methylated azoheteroarenes show that these photoswitches have potential in various optically addressable applications. The thermal stability of molecular switches is one of the primary factors considered in the design process. For molecular memory or energy storage devices, long thermal relaxation times are required. However, inducing a short thermal isomerization lifetime is required to release stored energy or as an alternative to photoswitching to avoid overlapping absorption spectra that reduce switching fidelity. In this study, we investigate how oriented external electric fields can be used to tune the thermal isomerization properties of three unsubstituted heteroaryl azo compounds-azoimidazole, azopyrazole, and azopyrrole. We show that favorable electric field orientations can increase the thermal half-life of studied molecules by as much as 60 times or reduce it from tens of days to seconds, compared to their half-life values in the field-free environment. A deeper understanding of the relationship between structure and kinetic properties provides insight as to how molecular switches can be designed for their electric field response in switching applications.

Orbital optimization in nonorthogonal multiconfigurational self-consistent field applied to the study of conical intersections and avoided crossings.

Nonorthogonal approaches to electronic structure methods have recently received renewed attention, with the hope that new forms of nonorthogonal wavefunction Ansätze may circumvent the computational bottleneck of orthogonal-based methods. The basis in which nonorthogonal configuration interaction is performed defines the compactness of the wavefunction description and hence the efficiency of the method. Within a molecular orbital approach, nonorthogonal configuration interaction is defined by a "different orbitals for different configurations" picture, with different methods being defined by their choice of determinant basis functions. However, identification of a suitable determinant basis is complicated, in practice, by (i) exponential scaling of the determinant space from which a suitable basis must be extracted, (ii) possible linear dependencies in the determinant basis, and (iii) inconsistent behavior in the determinant basis, such as disappearing or coalescing solutions, as a result of external perturbations, such as geometry change. An approach that avoids the aforementioned issues is to allow for basis determinant optimization starting from an arbitrarily constructed initial determinant set. In this work, we derive the equations required for performing such an optimization, extending previous work by accounting for changes in the orthogonality level (defined as the dimension of the orbital overlap kernel between two determinants) as a result of orbital perturbations. The performance of the resulting wavefunction for studying avoided crossings and conical intersections where strong correlation plays an important role is examined.

Effect of Oriented External Electric Fields on the Photo and Thermal Isomerization of Azobenzene.

Azobenzene is a prototype molecule with potential applications in molecular switches, solar thermal batteries, sensors, photoresponsive membranes, molecular electronics, data storage, and nonlinear optics. Photo and thermal isomerization pathways exhibit different charge-transfer character and dipole moments, implying that the use of electric fields can be used to modulate the reactivity of azobenzene. This article examines the differential effect of orientated electric fields on the rotation and inversion thermal and photoisomerization pathways of azobenzene to explore the feasibility of using electric fields in the design of azobenzene-based molecular devices. Our findings demonstrate that the application of orientated electric fields modifies the accessibility of the S0/S1 seam of electronic degeneracy, as well as changes the energetically favored relaxation pathway in the branching space to yield different photoproducts. In addition, we observed strong-field dipole-inversion effects that cause a topographical change in the response of the potential energy surface to the applied field and can result in geometric minima that do not exist under field-free conditions. On the S0 surface, transition barriers can be modified on the order of ±10 kcal mol-1, enabling control of thermal isomerization rates.

Difference projection-after-variation double-hybrid density functional theory applied to the calculation of vertical excitation energies.

The use of projection-after-variation double-hybrid density functional theory is proposed and examined as a difference method for the calculation of excited states. The strengths and weaknesses of the proposed method are discussed with particular reference to connections with linear response coupled-cluster theory. Vertical excitation energies are computed for the 28 molecule benchmark of Schreiber and co-workers in order to compare how the model performs with linear response coupled-cluster theories and multireference perturbation theory. The findings of this study show that the proposed method can achieve standard deviations in the error of computed vertical excitation energies compared to complete active space second-order perturbation theory of similar size to linear response coupled-cluster theories.

Etiological Distinction Across Dimensions of Math Anxiety.

Analyses have suggested math anxiety is a multidimensional construct. However, previous behavioral genetic work examining math anxiety was unidimensional. Thus, the purpose of the present study was to examine different approaches for specifying behavioral genetic models of math anxiety as a multidimensional construct. Three models were compared: a unidimensional model, a three dimension multidimensional model, and a bi-factor model, which partitioned variance into one common factor shared across three dimensions of math anxiety and examined residual variance in each dimension. The best fitting model was a bi-factor AE model, which suggested moderate heritability of general math anxiety and that each dimension of math anxiety had unique etiological influences not accounted for by shared variance with the general math anxiety factor. Thus, while there was evidence of shared etiology, there was also evidence of some etiological distinction across dimensions of math anxiety. The results demonstrate the importance of taking into account the dimensionality of the scale when interpreting similarity across twins.

The Influence of ß-Ammonium Substitution on the Reaction Kinetics of Aminooxy Condensations with Aldehydes and Ketones.

The click-chemistry capture of volatile aldehydes and ketones by ammonium aminooxy compounds has proven to be an efficient means of analyzing the carbonyl subset in complex mixtures, such as exhaled breath or environmental air. In this work, we examine the carbonyl condensation reaction kinetics of three aminooxy compounds with varying ß-ammonium ion substitution using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). We determined the activation energies for the reactions of the aminooxy compounds ATM, ADMH and AMAH with a panel of ketones and aldehydes that included acrolein and crotonaldehyde. The measurements indicate that the activation energies for the oximation reactions are quite low, less than 75 kJ mol-1 . ADMH is observed to react the fastest with the carbonyls studied. We postulate this result may be attributed to the ADMH ammonium proton effecting a Brønsted-Lowry acid-catalyzed elimination of water during the rate-determining step of oxime ether formation. A theoretical study of oxime ether formation is presented to explain the enhanced reactivity of ADMH relative to the tetraalkylammonium analog ATM.

On the linear geometry of lanthanide hydroxide (Ln-OH, Ln = La-Lu).

Lanthanide hydroxides are key species in a variety of catalytic processes and in the preparation of corresponding oxides. This work explores the fundamental structure and bonding of the simplest lanthanide hydroxide, LnOH (Ln = La-Lu), using density functional theory calculations. Interestingly, the calculations predict that all structures of this series will be linear. Furthermore, these results indicate a valence electron configuration of σ2π4 for all LnOH compounds, suggesting that the lanthanide-hydroxide bond is best characterized as a covalent triple bond.

Education setting-based health promotion in New Zealand: evaluating the wellbeing and vitality in education (WAVE) programme.

Wellbeing and vitality in education (WAVE) is an education setting based health promotion initiative in South Canterbury, New Zealand. A mixed method approach was used for assessing change over time. Over ninety percent of education settings (94%) were participating in WAVE (n = 95). A total of 73 education settings completed the questionnaire at both baseline and follow-up. Evaluation of the WAVE programme shows that a robust partnership between health and education sectors can provide the basis for high levels of participation and significant changes in practice across all levels of education and a whole province. Evaluation results included that professional development for staff in some health related topics had improved. There was evidence of increasing partnerships between schools and community. Teachers had become role models for health messages and students had taken on leadership roles. Although the approach was based on health promoting schools literature, early engagement with education settings allowed the development of a local programme and branding. The overall outcome of WAVE has been a culture change in South Canterbury, where promoting the health of students, staff and families is becoming part of normal business for education settings. The results provide reason for optimism regarding the careful use of a health promoting schools framework, working in partnership with a range of stakeholders towards improving the health and subsequent life chances of young people.

Multidimensionality in the Measurement of Math-Specific Anxiety and its Relationship with Mathematical Performance.

Traditionally, mathematical anxiety has been utilized as a unidimensional construct. However, math-specific anxiety may have distinguishable factors, and taking these factors into account may better illuminate the relationship between anxiety and mathematics performance. Drawing from the Western Reserve Reading and Math Project (N = 244 children, mean age = 12.28 years), the present study examined math-specific anxiety and mathematics problem evaluation, utilizing a structural equation modeling approach with an item-level measurement model structure. Results suggested math-specific anxiety tapped into three factors: anxiety about performing mathematical calculations, anxiety about math in classroom situations, and anxiety about math tests. Among the three math anxiety factors, only calculation anxiety was significantly and negatively related to math performance while holding other anxiety factors constant. Implications for the measurement of math-specific anxiety are discussed.

Passive, continuous monitoring of carbon dioxide geostorage using muon tomography.

Carbon capture and storage is a transition technology from a past and present fuelled by coal, oil and gas and a planned future dominated by renewable energy sources. The technology involves the capture of carbon dioxide emissions from fossil fuel power stations and other point sources, compression of the CO2 into a fluid, transporting it and injecting it deep beneath the Earth's surface into depleted petroleum reservoirs and other porous formations. Once injected, the CO2 must be monitored to ensure that it is emplaced and assimilated as planned and that none leaks back to surface. A variety of methods have been deployed to monitor the CO2 storage site and many such methods have been adapted from oilfield practice. However, such methods are commonly indirect, episodic, require active signal generation and remain expensive throughout the monitoring period that may last for hundreds of years. A modelling framework was developed to concurrently simulate CO2 geostorage conditions and background cosmic-ray muon tomography, in which the potential was assessed for using variations in muon attenuation, due to changes in CO2 abundance, as a means of CO2 detection. From this, we developed a passive, continuous monitoring method for CO2 storage sites using muon tomography, the tools for which can be deployed during the active drilling phase (development) of the storage site. To do this, it was necessary to develop a muon detector that could be used in the hostile environment (saline, high temperature) of the well bore. A prototype detector has been built and tested at the 1.1 km deep Boulby potash mine on the northeast coast of England, supported by the existing STFC Boulby Underground Laboratory on the site. The detector is now ready to be commercialized.This article is part of the Theo Murphy meeting issue 'Cosmic-ray muography'.

Global elucidation of broken symmetry solutions to the independent particle model through a Lie algebraic approach.

Broken symmetry solutions-solutions to the independent particle model that do not obey all symmetries required by the Hamiltonian-have attracted significant interest for capturing multireference properties with mean-field scaling. However, identification and optimization of broken-symmetry solutions is difficult owing to the non-linear nature of the self-consistent field (SCF) equations, particularly for solutions belonging to low-symmetry subgroups and where multiple broken symmetry solutions are sought. Linearization of SCF solution space results in the Lie algebra, which this work utilizes as a framework for elucidation of the set of solutions that exist at the desired symmetry. To demonstrate that searches constructed in the Lie algebra yield the set of broken symmetry solutions, a grid-based search of real-restricted, real-unrestricted, complex-restricted, paired-unrestricted, and real-general solutions of the C 2 v (nearly D 4h ) H4 molecule is performed.

Development in reading and math in children from different SES backgrounds: the moderating role of child temperament.

Socioeconomic risks (SES risks) are robust risk factors influencing children's academic development. However, it is unclear whether the effects of SES on academic development operate universally in all children equally or whether they vary differentially in children with particular characteristics. The current study aimed to explore children's temperament as protective or risk factors that potentially moderate the associations between SES risks and academic development. Specifically, latent growth modeling (LGM) was used in two longitudinal datasets with a total of 2236 children to examine how family SES risks and children's temperament interactively predicted the development of reading and math from middle childhood to early adolescence. Results showed that low negative affect, high effortful control, and low surgency mitigated the negative associations between SES risks and both reading and math development in this developmental period. These findings underline the heterogeneous nature of the negative associations between SES risks and academic development and highlight the importance of the interplay between biological and social factors on individual differences in development.

Explaining the MoVO4- photoelectron spectrum: Rationalization of geometric and electronic structure.

Attempts to reconcile simulated photoelectron spectra of MoVO4- clusters are complicated by the presence of very low energy barriers in the potential energy surfaces (PESs) of the lowest energy spin states and isomers. Transition state structures associated with the inversion of terminal oxygen ligands are found to lie below, or close to, the zero point energy of associated modes, which themselves are found to be of low frequency and thus likely to be significantly populated in the experimental characterization. Our simulations make use of Boltzmann averaging over low-energy coordinates and full mapping of the PES to obtain simulations in good agreement with experimental spectra. Furthermore, molecular orbital analysis of accessible final spin states reveals the existence of low energy two-electron transitions in which the final state is obtained from a finite excitation of an electron along with the main photodetachment event. Two-electron transitions are then used to justify the large difference in intensity between different bands present in the photoelectron spectrum. Owing to the general presence of terminal ligands in metal oxide clusters, this study identifies and proposes a solution to issues that are generally encountered when attempting to simulate transition metal cluster photoelectron spectroscopy.