Insights into localization, energy ordering, and substituent effect in excited states of azobenzenes from coupled cluster calculations of nuclear spin-induced circular dichroism.

Nuclear spin-induced circular dichroism (NSCD) is a molecular effect of differential absorption of left- and right-circularly polarized light due to nuclear spins in the molecule. In this work, new tools for its calculation are presented. Specifically, analytic expressions for the computation of the K term of NSCD have been derived and implemented for the second-order coupled cluster singles and doubles (CC2) model. NSCD results obtained thereby for three derivatives of azobenzenes have been compared with results from time-dependent density functional theory (TD-DFT). The complementary information that could be obtained from NSCD measurements compared to NMR for these three species is discussed.

Workplace sexual and gender-based harassment in Denmark: a comparison of the self-labelling and behavioural list method.

AIM: Knowledge about the prevalence of sexual and gender-based harassment is hampered by disagreements about definitions and measurement methods. The two most common measurement methods are the self-labelling (a single question about exposure to sexual harassment) and the behavioural list method (an inventory of sexually harassing behaviours). The aim of this paper was to compare the self-labelling and the behavioural list methods for measuring sexual harassment and assess the association with depressive symptoms. METHODS: The study is based on a convenience sample of 1686 individuals employed in 29 workplaces in Denmark. Survey data were collected from November 2020 until June 2021 and there were 1000 participants with full data on key variables. We used a linear mixed-effects model to examine the relationship between sexual harassment and depressive symptoms. RESULTS: In total, 2.5% self-labelled as being sexually harassed, while 19.0% reported exposure to at least one type of sexual and gender-based harassment using the behavioural list method. Both groups reported higher levels of depressive symptoms compared with non-exposed employees. The most common types of behaviours were: that someone spoke derogatorily about women/men (11.6%); being belittled because of one's gender or sexuality (4.7%); and unwanted comments about one's body, clothes or lifestyle (4.5%). CONCLUSIONS: The behavioural list method yielded a higher prevalence of sexual and gender-based harassment compared with the self-labelling method. Self-labelling and reporting at least one type of sexual and gender-based harassment was associated with depressive symptoms.

'We had conversations we wouldn't have had otherwise'-Exploring home-dwelling people with dementia and family members' experiences of deliberating on ethical issues in a literature-based intervention.

AIM: To explore home-dwelling people with dementia and family members' perceptions of the feasibility and acceptability of an intervention using dementia-related literature excerpts to facilitate conversations on ethical issues related to living with dementia. BACKGROUND: Ethical issues in dementia care emerge throughout the illness. In the early stages, they may involve decisions about disclosing the illness to the family, shifting roles and responsibilities, and considerations of transitioning to a nursing home. Addressing ethical issues and providing adequate support to home-dwelling people with dementia and their families are often lacking. DESIGN: An exploratory-descriptive qualitative study. METHODS: We conducted eight interviews with 14 home-dwelling persons with dementia and their family caregivers. Six were dyadic interviews, and two were individual interviews with family caregivers. We analysed the interview data using template analysis. We adhered to the COREQ checklist in reporting this study. RESULTS: Using excerpts from dementia-related literature was a feasible and acceptable way of initiating discussions on ethical issues among home-dwelling persons with dementia and family caregivers. However, engaging the families of newly diagnosed individuals was challenging due to emotional distress. The intervention provided peer support, including identifying with others and sharing experiences. Moreover, participating couples found intimacy and relational attunement through shared reflections. CONCLUSION: Based on the findings, it appears that the participants in this study felt that using excerpts from dementia-related literature to deliberate on ethical issues was feasible and acceptable. Deliberating on ethical issues with peers and family caregivers offers valuable social support and opportunities for strengthening relationships. IMPLICATIONS FOR PATIENT CARE: This study makes an important contribution by providing valuable insights into how ethical issues related to living with dementia can be addressed using related literature and suggests how the intervention can be integrated into existing care initiatives for home-dwelling people with dementia and their families. REPORTING METHOD: We have adhered to relevant EQUATOR guidelines with the COREQ reporting method. PATIENT OR PUBLIC CONTRIBUTION: A healthcare professional working as a so-called dementia coordinator (a title used in the Danish context) was involved in the conduct of this study by being responsible for the recruitment of home-dwelling people with dementia and their family members. Moreover, she had joint responsibility for facilitating the intervention along with the first author.

Linear response properties of solvated systems: a computational study.

We present a computational study of static and dynamic linear polarizabilities in solution. We use different theoretical approaches to describe solvent effects, ranging from quantum mechanics/molecular mechanics (QM/MM) to quantum embedding approaches. In particular, we consider non-polarizable and polarizable QM/MM methods, the latter based on the fluctuating charge (FQ) force field. In addition, we use a quantum embedding method defined in the context of multilevel Hartree-Fock (MLHF), where the system is divided into active and inactive regions, and combine it with a third layer described by means of the FQ model. The multiscale approaches are then used as reference wave functions for equation-of-motion coupled cluster (EOM-CC) response properties, allowing for the account of electron correlation. The developed models are applied to the calculation of linear response properties of two organic moieties-namely, para-nitroaniline and benzonitrile-in non-aqueous solvents-1,4-dioxane, acetonitrile, and tetrahydrofuran. The computed polarizabilities are then discussed in terms of the physico-chemical solute-solvent interactions described by each method (electrostatic, polarization and Pauli repulsion), and finally compared with the available experimental references.

Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.

eT 1.0: An open source electronic structure program with emphasis on coupled cluster and multilevel methods.

The eT program is an open source electronic structure package with emphasis on coupled cluster and multilevel methods. It includes efficient spin adapted implementations of ground and excited singlet states, as well as equation of motion oscillator strengths, for CCS, CC2, CCSD, and CC3. Furthermore, eT provides unique capabilities such as multilevel Hartree-Fock and multilevel CC2, real-time propagation for CCS and CCSD, and efficient CC3 oscillator strengths. With a coupled cluster code based on an efficient Cholesky decomposition algorithm for the electronic repulsion integrals, eT has similar advantages as codes using density fitting, but with strict error control. Here, we present the main features of the program and demonstrate its performance through example calculations. Because of its availability, performance, and unique capabilities, we expect eT to become a valuable resource to the electronic structure community.

A genome-wide association meta-analysis of diarrhoeal disease in young children identifies FUT2 locus and provides plausible biological pathways.

More than a million childhood diarrhoeal episodes occur worldwide each year, and in developed countries a considerable part of them are caused by viral infections. In this study, we aimed to search for genetic variants associated with diarrhoeal disease in young children by meta-analyzing genome-wide association studies, and to elucidate plausible biological mechanisms. The study was conducted in the context of the Early Genetics and Lifecourse Epidemiology (EAGLE) consortium. Data about diarrhoeal disease in two time windows (around 1 year of age and around 2 years of age) was obtained via parental questionnaires, doctor interviews or medical records. Standard quality control and statistical tests were applied to the 1000 Genomes imputed genotypic data. The meta-analysis (N = 5758) followed by replication (N = 3784) identified a genome-wide significant association between rs8111874 and diarrhoea at age 1 year. Conditional analysis suggested that the causal variant could be rs601338 (W154X) in the FUT2 gene. Children with the A allele, which results in a truncated FUT2 protein, had lower risk of diarrhoea. FUT2 participates in the production of histo-blood group antigens and has previously been implicated in the susceptibility to infections, including Rotavirus and Norovirus Gene-set enrichment analysis suggested pathways related to the histo-blood group antigen production, and the regulation of ion transport and blood pressure. Among others, the gastrointestinal tract, and the immune and neuro-secretory systems were detected as relevant organs. In summary, this genome-wide association meta-analysis suggests the implication of the FUT2 gene in diarrhoeal disease in young children from the general population.

Efficient Protocol for Computing MCD Spectra in a Broad Frequency Range Combining Resonant and Damped CC2 Quadratic Response Theory.

Coupled cluster response theory offers a path to high-accuracy calculations of spectroscopic properties, such as magnetic circular dichroism (MCD). However, divergence or slow convergence issues are often encountered for electronic transitions in high-energy regions with a high density of states. This is here addressed for MCD by an implementation of damped quadratic response theory for resolution-of-identity coupled cluster singles-and-approximate-doubles (RI-CC2), along with an implementation of the MCD A term from resonant response theory. Combined, damped and resonant response theory calculations provide an efficient strategy to obtain MCD spectra over a broad frequency range and for systems that include highly symmetric molecules with degenerate excited states. The protocol is illustrated by application to zinc tetrabenzoporphyrin in the energy region of 2-8 eV and comparison to experimental data. Timings are reported for the resonant and damped approaches, showing that a greater part of the calculation time is consumed by the construction of the building blocks for the final MCD ellipticity. A recommendation on how to use the procedure is outlined.

TURBOMOLE: Today and Tomorrow.

TURBOMOLE is a highly optimized software suite for large-scale quantum-chemical and materials science simulations of molecules, clusters, extended systems, and periodic solids. TURBOMOLE uses Gaussian basis sets and has been designed with robust and fast quantum-chemical applications in mind, ranging from homogeneous and heterogeneous catalysis to inorganic and organic chemistry and various types of spectroscopy, light-matter interactions, and biochemistry. This Perspective briefly surveys TURBOMOLE's functionality and highlights recent developments that have taken place between 2020 and 2023, comprising new electronic structure methods for molecules and solids, previously unavailable molecular properties, embedding, and molecular dynamics approaches. Select features under development are reviewed to illustrate the continuous growth of the program suite, including nuclear electronic orbital methods, Hartree-Fock-based adiabatic connection models, simplified time-dependent density functional theory, relativistic effects and magnetic properties, and multiscale modeling of optical properties.

Probing Molecular Chirality of Ground and Electronically Excited States in the UV-vis and X-ray Regimes: An EOM-CCSD Study.

We present several strategies for computing electronic circular dichroism (CD) spectra across different frequency ranges at the equation-of-motion coupled-cluster singles and doubles level of theory. CD spectra of both ground and electronically excited states are discussed. For selected cases, the approach is compared with coupled-cluster linear response results as well as time-dependent density functional theory. The extension of the theory to include the effect of spin-orbit coupling is presented and illustrated by calculations of X-ray CD spectra at the L-edge.

Cherry-Picking Resolvents: Recovering the Valence Contribution in X-ray Two-Photon Absorption within the Core-Valence-Separated Equation-of-Motion Coupled-Cluster Response Theory.

Calculations of first-order response wave functions in the X-ray regime often diverge within correlated frameworks such as equation-of-motion coupled-cluster singles and doubles (EOM-CCSD), a consequence of the coupling with the valence ionization continuum. Here, we extend our strategy of introducing a hierarchy of approximations to the EOM-EE-CCSD resolvent (or, inversely, the model Hamiltonian) involved in the response equations for the calculation of X-ray two-photon absorption (X2PA) cross sections. We exploit the frozen-core core-valence separation (fc-CVS) scheme to first decouple the core and valence Fock spaces, followed by a separate approximate treatment of the valence resolvent. We demonstrate the robust convergence of X-ray response calculations within this framework and compare X2PA spectra of small benchmark molecules with the previously reported density functional theory results.

Designing a conversational agent to promote teamwork and collaborative practices using design thinking: An explorative study on user experiences.

Appearance, voice features, and communication style affect users trust in conversational agents (chatbots), but few studies have assessed what features users like and dislike. Using design thinking, we developed Susa, a conversational agent, to help workplaces promote teamwork and collaborative practices. Design thinking prioritizes co-creation and multidisciplinary teamwork to develop innovative solutions to complex problems. The aim of this qualitative study was to explore users' interactions with and reactions toward Susa and explain how we used user inputs to adapt and refine the first prototype. The employees and managers from four workplaces participated in three workshops to test and refine the agent. We applied an explorative thematic analysis of data collected via video recordings of the workshops. The results of the analyses revealed that visual identity, communication style and personality was important for acceptability. Users favored a more human like agent that primarily communicated with the team via text messages. Users disliked emoticons and humor because these features clashed with the seriousness of the topic. Finally, users highlighted that Susa helped structure organizational change processes, develop concrete action plans, and stay on track. It is a weakness that Susa is a simple robot based on a preprogrammed script that does not allow users to adapt the process.

Motor Skills and Exercise Capacity Are Associated with Objective Measures of Cognitive Functions and Academic Performance in Preadolescent Children.

OBJECTIVE: To investigate associations between motor skills, exercise capacity and cognitive functions, and evaluate how they correlate to academic performance in mathematics and reading comprehension using standardised, objective tests. METHODS: This cross-sectional study included 423 Danish children (age: 9.29±0.35 years, 209 girls). Fine and gross motor skills were evaluated in a visuomotor accuracy-tracking task, and a whole-body coordination task, respectively. Exercise capacity was estimated from the Yo-Yo intermittent recovery level 1 children's test (YYIR1C). Selected tests from the Cambridge Neuropsychological Test Automated Battery (CANTAB) were used to assess different domains of cognitive functions, including sustained attention, spatial working memory, episodic and semantic memory, and processing speed. Linear mixed-effects models were used to investigate associations between these measures and the relationship with standard tests of academic performance in mathematics and reading comprehension. RESULTS: Both fine and gross motor skills were associated with better performance in all five tested cognitive domains (all P<0.001), whereas exercise capacity was only associated with better sustained attention (P<0.046) and spatial working memory (P<0.038). Fine and gross motor skills (all P<0.001), exercise capacity and cognitive functions such as working memory, episodic memory, sustained attention and processing speed were all associated with better performance in mathematics and reading comprehension. CONCLUSIONS: The data demonstrate that fine and gross motor skills are positively correlated with several aspects of cognitive functions and with academic performance in both mathematics and reading comprehension. Moreover, exercise capacity was associated with academic performance and performance in some cognitive domains. Future interventions should investigate associations between changes in motor skills, exercise capacity, cognitive functions, and academic performance to elucidate the causality of these associations.