Your phrases matter: Third waves in research approaches and new contexts for formulaic language.

BACKGROUND: This study reports on new contexts in which formulaic language has been used in the years since 2013 when the last synthesis was carried out. The background presents an old but still useful definition and lists themes under which research was arranged in 2013 and which continue to be used. AIMS: This study has a particular emphasis on the relevance of formulaic language to people living with dementia. METHODS: Section 3, identifying new directions, reviews new 'third waves' of research priorities in several fields in which formulaic sequences play a major role, including sociolinguistic variation, corpus-based and corpus-driven analyses, pragmatics, human-computer interaction, and psycholinguistics, all of which are relevant to speech-language therapists. Section 4, outreach and expansions, illustrates new contributions from cognitively impaired person-to-person exchanges in online environments, recent examinations of infant- and pet-directed speech incorporating formulaic language, and online graphic explorations such as emojis. Section 5 focuses on growth of research in theoretical and clinical applications by Van Lancker Sidtis, as illustrated by references to her recent work. MAIN CONTRIBUTION: The paper's main contribution is to summarize the work on formulaic language over the last 10 years, to indicate its continued importance and relevance in ordinary conversation, and especially in allowing people living with dementia to continue to interact with others. CONCLUSION: The paper concludes by suggesting that more focus be placed on the analysis of formulaic language with an emphasis on its relevance for speech-language therapists and other clinicians. WHAT THIS PAPER ADDS: What is already known on the subject Research has been growing since the late 1970s and early 1980s on non-propositional language (as opposed at that time to the Chomskyan paradigm) and especially on lexical bundles, idioms, second language acquisition and multiword expressions. Studies beginning with Hughlings Jackson (1874) have been annotated through early 2012 (Wray, 2013). What this study adds This study examines 'third waves' in pragmatics, sociolinguistics and areas of neurology and speech perception contributing to what Van Lancker Sidtis (2021) calls the third wave of acceptance of the range and depth of formulaic sequences in ordinary or familiar language. What are the clinical implications of this work? Conversations with pet robots or web-based composition with emojis are but two of the developing areas built on formulaic sequences currently being used for communication interventions with persons living with dementia or other major neurocognitive disorder. Overviews of major contributions in theory and social contexts by Wray (2020, 2021) and theoretical and cognitive applications by Van Lancker Sidtis (2021) detail new areas for the study of formulaic sequences and their contributions to a range of neurocognitive disorders.

Influences of Faith on Rural Appalachian Older Adult Health: An Ethnonursing Study.

INTRODUCTION: Rural Appalachian older adults (RAOAs) constitute a vulnerable population and experience significant health disparities. The combination of age, poverty, rural residence, health care provider shortages, and limited transportation increases risks for poor health outcomes. Spirituality enhances older adult health; however, little is known about spirituality-health linkages of RAOAs. Therefore, the purpose of this study was to discover the influences of spirituality on RAOA health. METHODOLOGY: Culture Care Theory and ethnonursing method guided analysis of 32 RAOA interviews in community settings in East Tennessee. RESULTS: "Faith" is an integral component of RAOA culture and health. Three themes were extrapolated: (a) Relationship with God is personal; (b) faith beliefs and practices influence health, illness, death, and dying; and [the need to] (c) "Open the door" for spiritual care. DISCUSSION: Faith assessment and spiritual care recommendations contribute to culturally congruent care for RAOAs and may be transferable to care for other older adults.

"Turn It over to God": Faith Enhances Mental Health of Rural Appalachian Older Adults.

In Appalachia, rates of depression and suicidality are higher than national averages. Additional disparities of age, geographic isolation, economic distress, and mental healthcare provider shortages contribute to mental health challenges among rural Appalachian older adults (RAOAs). Based on ethnonursing research in East Tennessee, this article expands on findings about how RAOA faith beliefs and practices enhance mental health. Faith was found to decrease worry, improve coping, facilitate a sense of peace, and deepen thankfulness and joy. Implications for nursing practice and education indicate the importance of providing spiritual care to promote mental health and well-being for this vulnerable population.

Photophysical oxidation of HCHO produces HO2 radicals.

Formaldehyde, HCHO, is the highest-volume carbonyl in the atmosphere. It absorbs sunlight at wavelengths shorter than 330 nm and photolyses to form H and HCO radicals, which then react with O2 to form HO2. Here we show HCHO has an additional HO2 formation pathway. At photolysis energies below the energetic threshold for radical formation we directly detect HO2 at low pressures by cavity ring-down spectroscopy and indirectly detect HO2 at 1 bar by Fourier-transform infrared spectroscopy end-product analysis. Supported by electronic structure theory and master equation simulations, we attribute this HO2 to photophysical oxidation (PPO): photoexcited HCHO relaxes non-radiatively to the ground electronic state where the far-from-equilibrium, vibrationally activated HCHO molecules react with thermal O2. PPO is likely to be a general mechanism in tropospheric chemistry and, unlike photolysis, PPO will increase with increasing O2 pressure.

Relationships between Interpersonal Goals and Loneliness in Older Adults: A Cross-Sectional Study.

Loneliness is linked to many physiological and psychological issues and disproportionately affects older adults. Interpersonal goals (compassion and self-image) are essential to interpersonal relationships; however, how they relate to loneliness in older adults is unknown. We investigated the impact of interpersonal goals on loneliness using the Ecosystem-Egosystem Theory of Social Motivation. This study, adopting a descriptive cross-sectional correlational design, used data from the 2016 Health and Retirement Study. Participants (n = 3212) included people aged >65 years (mean age: 75; female: 60.1%). We performed exploratory factor analysis with principal axis factoring and varimax rotation to examine the suitability of compassionate and self-image goals as separate factors. The complex samples general linear model was used to assess the relationship between loneliness and interpersonal goals. Interpersonal goals were significantly negatively associated with loneliness. Respondents with higher compassion and self-image goals reported lower loneliness levels. Our results contribute to understanding how interpersonal goals relate to loneliness in older adults. These initial findings warrant further investigation.

Influence of Spiritual Engagement on Appalachian Older Adults' Health: A Systematic Review.

Appalachia leads the country in mortality related to chronic comorbidities, such as heart disease, cancer, depression, and suicide. Appalachian older adults experience disproportionate risks for poor health outcomes. Spirituality is integral to Appalachian culture, and many older adults use spiritual engagement (SE) to cope with health challenges. Despite these connections, there is limited evidence about SE and well-being in this population. Therefore, the current systematic review addresses the literature gap of how SE influences health of Appalachian older adults. Using thematic synthesis, we analyzed 11 qualitative and three mixed methods studies. Major findings indicate that SE positively impacts holistic health through adaptive coping, guided partnerships with God, decreased loneliness, and enhanced sense of purpose. Future studies could examine SE practices among diverse populations, SE virtual experiences, and SE nursing assessments. Understanding how SE influences health of Appalachian older adults could prepare nurses to reduce disparities and improve health outcomes for this vulnerable population. [Journal of Psychosocial Nursing and Mental Health Services, 61(5), 45-52.].

Older Adults' Views and Attitudes on Physical Activity; Reasons to Participate and Abstain.

Purpose: Despite numerous established benefits of exercise, many older adults do not get enough. The purpose of this study was to identify facilitators and barriers to physical activity/exercise; gain greater understanding of older adults' physical activity self-efficacy; and increase understanding of how to reduce sedentary behavior.Design: Cross-sectional descriptiveMethods: Quantitative with convenience sample of 66 older adultsFindings: Nearly one third of participants reported engaging in regular physical activity. They tended to have rather strong physical activity self-efficacy and limited barriers to being active.Conclusions: The sample had limited involvement in physical activity or exercise, despite feeling confident in their ability to be active. There could be additional barriers or motivating factors that are preventing them from being more active.Clinical Evidence: Honest and directed conversation about older adults' understanding and attitudes towards exercise, paired with an individualized plan tailored to their interests and lifestyle could help increase physical activity/exercise.

Effectiveness of eHealth Technology-Based Interventions in Reducing Substance Misuse Among Older Adults: A Systematic Review.

Generally considered an epidemic among young people, substance misuse has been a growing issue among older Americans for the past 40 years. Legal substances, such as alcohol, tobacco, and prescription drugs, including opioids and marijuana, are of primary concern when it comes to aging Baby Boomers. By 2050, 22% of Americans will be aged ≥65 years. Currently, eHealth interventions are receiving attention in treating substance misuse among younger Americans. The current study has two aims: to evaluate the effectiveness of eHealth interventions for older adults treated for substance misuse problems, as well as to investigate behavioral outcomes in reducing substance misuse. A comprehensive search of databases yielded 35,041 articles that examined reductions in substance misuse and problem behaviors as a primary outcome with eHealth interventions delivered to older adults. Once duplicate and irrelevant articles were removed, seven were left to be analyzed. Findings suggest use of technology to assess and intervene with older adults using various substances shows promise and, as a whole, older adults are receptive to online learning, screening and assessment, and interventions. [Journal of Gerontological Nursing, 47(10), 23-29.].

Rotational resonances in the H2CO roaming reaction are revealed by detailed correlations.

Since its discovery 16 years ago, roaming has become a ubiquitous mechanism in molecular photochemistry. Its general features are now understood, but little detail is known about how the potential energy surface (PES) determines reaction outcomes. We performed detailed experiments on formaldehyde (H2CO) photodissociation and determined fully correlated quantum state distributions of the molecular hydrogen and carbon monoxide products. These experiments reveal previously undetected bimodal carbon monoxide rotational distributions. Insights from classical trajectory calculations demonstrate that these features arise from resonances as the PES directs the reaction into cis and trans O-C-H···H critical geometries, which produce rebound and stripping mechanisms, respectively. These subtle and pervasive effects demonstrate additional complexity in this prototypical roaming reaction, which we expect to be general. They also provide detailed benchmarks for predictive theories of roaming.

Physical activity, cardiovascular health and mood state in older adults.

Many older adults eat poorly balanced diets and are physically inactive, posing a risk to their cardiovascular and mental health. The benefits of healthful living extend beyond cardiovascular health and disease risk reduction such that physical activity has been shown to positively affect mood state. This was a cross-sectional investigation completed at three senior lunch program sites in Charlotte, NC to assess the status and relationship of nutrition, physical activity patterns, and mood state in older adults, prior to the center offering a new nutritional and physical activity intervention. Some significant relationships between cardiovascular indicators and mood were found.

Structural Effects on the Norrish Type I α-Bond Cleavage of Tropospherically Important Carbonyls.

Norrish Type I (NTI) α-bond cleavage is the dominant photolysis mechanism in small carbonyls and is an important source of radicals in the troposphere. In nonsymmetric species two cleavages are possible, NTIa and NTIb, forming larger and smaller alkyl radicals, respectively. For a data set of 20 small, atmospherically relevant carbonyls we predict NTIa and NTIb thresholds on the S0, S1, and T1 electronic states. The calculated NTIa T1 thresholds give a mean absolute deviation (MAD) of 5.8 kJ/mol with respect to the available experimental thresholds of five carbonyls. In addition, the intrinsic barrier heights to dissociation on the S0, S1, and T1 electronic states are predicted. We find RI-B2GP-PLYP/def2-TZVP calculations on S0 and unrestricted RI-B2GP-PLYP/def2-TZVP calculations on T1 give MADs of 6.1 kJ/mol for S0 asymptotic energies and 6.3 kJ/mol for S0 → T1 0-0 excitation energies, with respect to available experimental data. A composite method is used to determine S1 thresholds, with bt-STEOM-CCSD/cc-pVQZ calculation of vertical excitation energies and TD-RI-B3LYP/def2-TZVP calculations on S1, which achieves a MAD of 7.2 kJ/mol, with respect to experimental 0-0 excitation energies. Our calculations suggest, with the exception of bifunctional carbonyls and enones, NTI reactions on S1 are unlikely to be important at tropospherically relevant photolysis energies (<400 kJ/mol). In contrast, at these energies almost all possible NTI channels on T1 are open, and all barrierless S0 NTI dissociations are accessible. Our calculations allow a number of structural effects on both 0-0 excitation energies and intrinsic reaction barriers, on a given electronic state, to be elucidated and rationalized.

Nutrients mediate the effects of temperature on methylmercury concentrations in freshwater zooplankton.

Methylmercury (MeHg) bioaccumulation in freshwater aquatic systems is impacted by anthropogenic stressors, including climate change and nutrient enrichment. The goal of this study was to determine how warmer water temperatures and excess nutrients would alter zooplankton communities and phytoplankton concentrations, and whether those changes would in turn increase or decrease MeHg concentrations in freshwater zooplankton. To test this, we employed a 2 × 2 factorial experimental design with nutrient and temperature treatments. Mesocosms were filled with ambient water and plankton from Cottage Grove Reservoir, Oregon, U.S.A., a waterbody that has experienced decades of elevated MeHg concentrations and corresponding fish consumption advisories due to run-off from Black Butte Mine tailings, located within the watershed. Treatment combinations of warmer temperature (increased by 0.7 °C), nutrient addition (a single pulse of 10× ambient concentrations of nitrogen and phosphorous), control, and a combination of temperature and nutrients were applied to mesocosms. The individual treatments altered phytoplankton densities and community structure, but alone the effects on MeHg concentrations were muted. Importantly, we found a significant interactive effect of nutrients and temperature: the nutrient addition appeared to buffer against increased MeHg concentrations associated with elevated temperature. However, there was variability in this response, which seems to be related to the abundance of Daphnia and edible phytoplankton. Nutrients at low temperature were associated with marginal increases (1.1×) in zooplankton MeHg. Our findings suggest that global change drivers that influence community composition and ecosystem energetics of both zooplankton and phytoplankton can alter MeHg pathways through food webs.

Dynamics and quantum yields of H2 + CH2CO as a primary photolysis channel in CH3CHO.

The first experimental observation of the primary photochemical channel of acetaldehyde leading to the formation of ketene (CH2CO) and hydrogen (H2) molecular products is reported. Acetaldehyde (CH3CHO) was photolysed in a molecular beam at 305.6 nm and the resulting H2 product characterized using velocity-map ion (VMI) imaging. Resonance-enhanced multiphoton ionization (REMPI), via two-photon excitation to the double-well EF 1Σ state, was used to state-selectively ionize the H2 and determine angular momentum distributions for H2 (ν = 0) and H2 (ν = 1). Velocity-map ion images were obtained for H2 (ν = 0 and 1, J = 5), allowing the total translational energy release of the photodissociation process to be determined. Following photolysis of CH3CHO in a gas cell, the CH2CO co-fragment was identified, using Fourier transform infrared spectroscopy, by its characteristic infrared absorption at 2150 cm-1. The measured quantum yield of the CH2CO + H2 product channel at 305.0 nm is φ = 0.0075 ± 0.0025 for both 15 Torr of neat CH3CHO and a mixture with 745 Torr of N2. Although small, this result has implications for the atmospheric photochemistry of carbonyls and this reaction represents a new tropospheric source of H2. Quasi-classical trajectory (QCT) simulations on a zero-point energy corrected reaction-path potential are also performed. The experimental REMPI and VMI image distributions are not consistent with the QCT simulations, indicating a non reaction-path mechanism should be considered.

Zero-point energy conservation in classical trajectory simulations: Application to H2CO.

A new approach for preventing zero-point energy (ZPE) violation in quasi-classical trajectory (QCT) simulations is presented and applied to H2CO "roaming" reactions. Zero-point energy may be problematic in roaming reactions because they occur at or near bond dissociation thresholds and these channels may be incorrectly open or closed depending on if, or how, ZPE has been treated. Here we run QCT simulations on a "ZPE-corrected" potential energy surface defined as the sum of the molecular potential energy surface (PES) and the global harmonic ZPE surface. Five different harmonic ZPE estimates are examined with four, on average, giving values within 4 kJ/mol-chemical accuracy-for H2CO. The local harmonic ZPE, at arbitrary molecular configurations, is subsequently defined in terms of "projected" Cartesian coordinates and a global ZPE "surface" is constructed using Shepard interpolation. This, combined with a second-order modified Shepard interpolated PES, V, allows us to construct a proof-of-concept ZPE-corrected PES for H2CO, V eff, at no additional computational cost to the PES itself. Both V and V eff are used to model product state distributions from the H + HCO → H2 + CO abstraction reaction, which are shown to reproduce the literature roaming product state distributions. Our ZPE-corrected PES allows all trajectories to be analysed, whereas, in previous simulations, a significant proportion was discarded because of ZPE violation. We find ZPE has little effect on product rotational distributions, validating previous QCT simulations. Running trajectories on V, however, shifts the product kinetic energy release to higher energy than on V eff and classical simulations of kinetic energy release should therefore be viewed with caution.

Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere.

Organic acids play a key role in the troposphere, contributing to atmospheric aqueous-phase chemistry, aerosol formation, and precipitation acidity. Atmospheric models currently account for less than half the observed, globally averaged formic acid loading. Here we report that acetaldehyde photo-tautomerizes to vinyl alcohol under atmospherically relevant pressures of nitrogen, in the actinic wavelength range, λ = 300-330 nm, with measured quantum yields of 2-25%. Recent theoretical kinetics studies show hydroxyl-initiated oxidation of vinyl alcohol produces formic acid. Adding these pathways to an atmospheric chemistry box model (Master Chemical Mechanism) demonstrates increased formic acid concentrations by a factor of ~1.7 in the polluted troposphere and a factor of ~3 under pristine conditions. Incorporating this mechanism into the GEOS-Chem 3D global chemical transport model reveals an estimated 7% contribution to worldwide formic acid production, with up to 60% of the total modeled formic acid production over oceans arising from photo-tautomerization.

Path integrals with higher order actions: Application to realistic chemical systems.

Quantum thermodynamic parameters can be determined using path integral Monte Carlo (PIMC) simulations. These simulations, however, become computationally demanding as the quantum nature of the system increases, although their efficiency can be improved by using higher order approximations to the thermal density matrix, specifically the action. Here we compare the standard, primitive approximation to the action (PA) and three higher order approximations, the Takahashi-Imada action (TIA), the Suzuki-Chin action (SCA) and the Chin action (CA). The resulting PIMC methods are applied to two realistic potential energy surfaces, for H2O and HCN-HNC, both of which are spectroscopically accurate and contain three-body interactions. We further numerically optimise, for each potential, the SCA parameter and the two free parameters in the CA, obtaining more significant improvements in efficiency than seen previously in the literature. For both H2O and HCN-HNC, accounting for all required potential and force evaluations, the optimised CA formalism is approximately twice as efficient as the TIA formalism and approximately an order of magnitude more efficient than the PA. The optimised SCA formalism shows similar efficiency gains to the CA for HCN-HNC but has similar efficiency to the TIA for H2O at low temperature. In H2O and HCN-HNC systems, the optimal value of the a1 CA parameter is approximately 13, corresponding to an equal weighting of all force terms in the thermal density matrix, and similar to previous studies, the optimal α parameter in the SCA was ∼0.31. Importantly, poor choice of parameter significantly degrades the performance of the SCA and CA methods. In particular, for the CA, setting a1 = 0 is not efficient: the reduction in convergence efficiency is not offset by the lower number of force evaluations. We also find that the harmonic approximation to the CA parameters, whilst providing a fourth order approximation to the action, is not optimal for these realistic potentials: numerical optimisation leads to better approximate cancellation of the fifth order terms, with deviation between the harmonic and numerically optimised parameters more marked in the more quantum H2O system. This suggests that numerically optimising the CA or SCA parameters, which can be done at high temperature, will be important in fully realising the efficiency gains of these formalisms for realistic potentials.

The energy dependence of CO(v,J) produced from H2CO via the transition state, roaming, and triple fragmentation channels.

The dynamics of CO production from photolysis of H2CO have been explored over a 8000 cm-1 energy range (345 nm-266 nm). Two-dimensional ion imaging, which simultaneously measures the speed and angular momentum distribution of a photofragment, was used to characterise the distribution of rotational and translational energy and to quantify the branching fraction of roaming, transition state (TS), and triple fragmentation (3F) pathways. The rotational distribution for the TS channel broadens significantly with increasing energy, while the distribution is relatively constant for the roaming channel. The branching fraction from roaming is also relatively constant at 20% of the observed CO. Above the 3F threshold, roaming decreases in favour of triple fragmentation. Combining the present data with our previous study on the H-atom branching fractions and published quantum yields for radical and molecular channels, absolute quantum yields were determined for all five dissociation channels for the entire S1←S0 absorption band, covering almost 8000 cm-1 of excitation energy. The S0 radical and TS molecular channels are the most important over this energy range. The absolute quantum yield of roaming is fairly constant ∼5% at all energies. The T1 radical channel is important (20%-40%) between 1500 and 4000 cm-1 above the H + HCO threshold, but becomes unimportant at higher energy. Triple fragmentation increases rapidly above its threshold reaching a maximum of 5% of the total product yield at the highest energy.

Infrared Spectra of Gas-Phase 1- and 2-Propenol Isomers.

Fourier transform infrared spectra of isolated 1-propenol and 2-propenol in the gas-phase have been collected in the range of 900-3800 cm-1, and the absolute infrared absorption cross sections reported for the first time. Both cis and trans isomers of 1-propenol were observed with the trans isomer in greater abundance. Syn and anti conformers of both 1- and 2-propenol were also observed, with abundance consistent with thermal population. The FTIR spectrum of the smaller ethenol (vinyl alcohol) was used as a benchmark for our computational results. As a consequence, its spectrum has been partially reassigned resulting in the first report of the anti-ethenol conformer. Electronic structure calculations were used to support our experimental results and assign vibrational modes for the most abundant isomers, syn-trans-1-propenol and syn-2-propenol.