Building citizen science intelligence for outbreak preparedness and response: a mixed-method study in nine countries to assess knowledge, readiness and feasibility.

INTRODUCTION: Citizen science (CS) is an emerging approach in public health to harness the collective intelligence of individuals to augment traditional scientific efforts. However, citizens' viewpoint, especially the hard-to-reach population, is lacking in current outbreak-related literature. We aim to understand the awareness, readiness and feasibility of outbreak-related CS, including digitally enabled CS, in low-income and middle-income countries. METHODS: This mixed-method study was conducted in nine countries between October 2022 and June 2023. Recruitment through civil society targeted the general population, marginalised/indigenous groups, youth and community health workers. Participants (aged ≥18 years) completed a quantitative survey, and a subset participated in focus group discussions (FGDs). RESULTS: 2912 participants completed the survey and 4 FGDs were conducted in each country. Incorporating participants' perspectives, CS is defined as the practice of active public participation, collaboration and communication in all aspects of scientific research to increase public knowledge, create awareness, build trust and facilitate information flow between citizens, governments and scientists. In Bangladesh, Indonesia, the Philippines, Cameroon and Kenya, majority were unaware of outbreak-related CS. In India and Uganda, majority were aware but unengaged, while in Nepal and Zimbabwe, majority participated in CS before. Engagement approaches should consider different social and cultural contexts, while addressing incentivisation, attitudes and practicality factors. Overall, 76.0% expressed interest in digital CS but needed training to build skills and confidence. Digital CS was perceived as convenient, safer for outbreak-related activities and producing better quality and quantity of data. However, there were concerns over non-inclusion of certain groups, data security and unclear communication. CONCLUSION: CS interventions need to be relatable and address context-specific factors influencing CS participation. Digital CS has the potential to facilitate collaboration, but capacity and access issues must be considered to ensure inclusive and sustainable engagement.

Structural Equation Model for Social Support and Quality of Life Among Individuals With Mental Health Disorders During the COVID-19 Pandemic.

BACKGROUND: In light of the COVID-19 pandemic, the distribution of social support for mental health problems has likely become unequal. Family- and community-based social support has been recognized as a promising approach for mental disorders; however, limited global frameworks have been applied to developing countries such as Vietnam. OBJECTIVE: The aim of this study was to evaluate the quality of life and social support among patients with mental health disorders in Vietnam and to investigate the factors associated with quality of life among these patients. METHODS: A cross-sectional study was conducted on 222 psychiatric patients in Hanoi from 2020 to 2022. A structured questionnaire was developed based on four standardized scales: Mental Well-Being-5 scale, Multidimensional Scale of Perceived Social Support, EuroQoL-visual analog scale (EQ-VAS), and EuroQoL-5 dimensions-5 levels (EQ-5D-5L) scale. Tobit regression was used to identify factors associated with the EQ-5D-5L and EQ-VAS scores. Structural equation modeling was applied to verify the relationship between quality of life and social support. RESULTS: The results showed that perceived support from family scored the highest compared to support from friends and significant others. Patients with depression reported the lowest quality of life and perceived social support. Structural equation modeling showed a root mean square error of approximation of 0.055 (90% CI 0.006-0.090), comparative fit index of 0.954, Tucker-Lewis index of 0.892, and standardized root mean squared error of 0.036 (P<.001). The hypothetical model indicated statistically significant correlations between EQ-VAS score and social support (P=.004), EQ-5D-5L and mental well-being (P<.001), and social support and mental well-being (P<.001). Critical deterioration of quality of life and inconsistency in social support for patients with mental illness were also recorded. CONCLUSIONS: There is a need to enhance social support and service delivery in Vietnam, focusing on occupation and quality of life. The correlations between social support, quality of life, and mental health issues suggest the potential of a clinical-social integrated intervention model of care.

An empirical potential for simulating hydrogen isotope retention in highly irradiated tungsten.

We describe the parameterization of a tungsten-hydrogen empirical potential designed for use with large-scale molecular dynamics simulations of highly irradiated tungsten containing hydrogen isotope atoms, and report test results. Particular attention has been paid to getting good elastic properties, including the relaxation volumes of small defect clusters, and to the interaction energy between hydrogen isotopes and typical irradiation-induced defects in tungsten. We conclude that the energy ordering of defects changes with the ratio of H atoms to point defects, indicating that this potential is suitable for exploring mechanisms of trap mutation, including vacancy loop to plate-like void transformations.

Preference and Willingness to Pay for the Regular COVID-19 Booster Shot in the Vietnamese Population: Theory-Driven Discrete Choice Experiment.

BACKGROUND: The COVID-19 booster vaccination rate has declined despite the wide availability of vaccines. As COVID-19 is becoming endemic and charges for regular booster vaccination are being introduced, measuring public acceptance and the willingness to pay for regular COVID-19 boosters is ever more crucial. OBJECTIVE: This study aims to (1) investigate public acceptance for regular COVID-19 boosters, (2) assess the willingness to pay for a COVID-19 booster shot, and (3) identify factors associated with vaccine hesitancy. Our results will provide crucial insights into and implications for policy response as well as the development of a feasible and effective vaccination campaign during Vietnam's waning vaccine immunity period. METHODS: A cross-sectional study was conducted among 871 Vietnamese online participants from April to August 2022. An online questionnaire based on the discrete choice experiment (DCE) design was developed, distributed using the snowball sampling method, and subsequently conjointly analyzed on the Qualtrics platform. A history of COVID-19 infection and vaccination, health status, willingness to vaccinate, willingness to pay, and other factors were examined. RESULTS: Among the participants, 761 (87.4%) had received or were waiting for a COVID-19 booster shot. However, the willingness to pay was low at US $8.02, and most participants indicated an unwillingness to pay (n=225, 25.8%) or a willingness to pay for only half of the vaccine costs (n=222, 25.4%). Although information insufficiency and a wariness toward vaccines were factors most associated with the unwillingness to pay, long-term side effects, immunity duration, and mortality rate were the attributes the participants were most concerned with during the vaccine decision-making period. Participants who had children less than 18 years old in their homes infected with COVID-19 had a lower willingness to pay (odds ratio [OR] 0.54, 95% CI 0.39-0.74). Respondents who had children under 12 years old in their family who received at least 1 vaccine dose had a higher willingness to pay (OR 2.03, 95% CI 1.12-3.66). The burden of medical expenses (OR 0.33, 95% CI 0.25-0.45) and fear of the vaccine (OR 0.93, 95% CI 0.86-1.00) were negative factors associated with the level of willingness to pay. CONCLUSIONS: A significant inconsistency between high acceptance and a low willingness to pay underscores the role of vaccine information and public trust. In addition to raising awareness about the most concerning characteristics of the COVID-19 booster, social media and social listening should be used in collaboration with health professionals to establish a 2-way information exchange. Work incentives and suitable mandates should continue to encourage workforce participation. Most importantly, all interventions should be conducted with informational transparency to strengthen trust between the public and authorities.

A comparative study of receptor interactions between SARS-CoV and SARS-CoV-2 from molecular modeling.

The pandemic of COVID-19 severe acute respiratory syndrome, which was fatal for millions of people worldwide, triggered the race to understand in detail the molecular mechanisms of this disease. In this work, the differences of interactions between the SARS-CoV/SARS-CoV-2 Receptor binding domain (RBD) and the human Angiotensin Converting Enzyme 2 (ACE2) receptor were studied using in silico tools. Our results show that SARS-CoV-2 RBD is more stable and forms more interactions with ACE2 than SARS-CoV. At its interface, three stable binding patterns are observed and named red-K31, green-K353 and blue-M82 according to the central ACE2 binding residue. In SARS-CoV instead, only the first two binding patches are persistently formed during the MD simulation. Our MM/GBSA calculations indicate the binding free energy difference of about 2.5 kcal/mol between SARS-CoV-2 and SARS-CoV which is compatible with the experiments. The binding free energy decomposition points out that SARS-CoV-2 RBD-ACE2 interactions of the red-K31 ([Formula: see text]) and blue-M82 ([Formula: see text]) patterns contribute more to the binding affinity than in SARS-CoV ([Formula: see text] for red-K31), while the contribution of the green-K353 pattern is very similar in the two strains ([Formula: see text] and [Formula: see text] for SARS-CoV-2 and SARS-CoV, respectively). Five groups of mutations draw our attention at the RBD-ACE2 binding interface, among them, the mutation -PPA469-471/GVEG482-485 has the most important and favorable impact on SARS-CoV-2 binding to the ACE2 receptor. These results, highlighting the molecular differences in the binding between the two viruses, contribute to the common knowledge about the new corona virus and to the development of appropriate antiviral treatments, addressing the necessity of ongoing pandemics.

Entomological survey in two communes with residual malaria transmission in Gia Lai Province in the central highlands of Vietnam.

BACKGROUND: In 2018, the National Malaria Control Programme in Vietnam switched from prioritizing malaria control to elimination. However, with the ongoing elimination programme, there are still areas where residual malaria transmission persists, including the central highlands. This entomological survey was conducted to evaluate Anopheles diversity and host-seeking activity of Anopheles vectors in two communes with very low malaria transmission in Gia Lai Province. METHODS: Anopheles species were collected in Ia DReh commune and Ia KDam commune, Gia Lai Province in the central highlands of Vietnam. Collections were conducted using human-baited double net trap, light trap and manual aspiration collections around cattle sheds, in the dry and rainy season. Mosquito specimens were identified morphologically, and members of species complexes were distinguished molecularly. Mosquito night-feeding patterns were investigated during the dry and rainy seasons. RESULTS: Overall, 18,835 specimens including 19 taxa were collected in Ia KDam and Ia DReh communes. These included the primary malaria vectors, Anopheles dirus and Anopheles minimus, and other secondary vector species. Anopheles dirus was observed to be an anthropophilic species, whereas An. minimus and a number of secondary vectors were observed to be zoophilic. Anopheles vagus was the dominant species, followed by Anopheles sinensis and Anopheles peditaeniatus. The majority of specimens were collected in the rainy season due to the relatively large number of An. vagus, while An. peditaeniatus, An. dirus, Anopheles kochi, Anopheles monstrosus and Anopheles tessellatus were collected in greater numbers during the dry season. The peak of host-seeking activity for An. dirus, An. sinensis, and An. vagus was between 18.00 and 19.00 h. CONCLUSION: This study provided information on the diversity, seasonal prevalence and behaviour of Anopheles at the study sites. Identifying the diverse mosquito fauna in the central highlands of Vietnam allows species-specific control measures to be implemented by the National Programme to reduce malaria in areas of very low malaria transmission. The peak Anopheles host-seeking activity observed in this study was between 18.00 and 23.00 h, which highlights the need to better characterize Anopheles behaviour in this region of Vietnam to inform on vector control strategies.

Effect of axial molecules and linker length on CO2 adsorption and selectivity of CAU-8: a combined DFT and GCMC simulation study.

Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) calculations are performed to study the structures and carbon dioxide (CO2) adsorption properties of the newly designed metal-organic framework based on the CAU-8 (CAU stands for Christian-Albrechts Universität) prototype. In the new MOFs, the 4,4'-benzophenonedicarboxylic acid (H2BPDC) linker of CAU-8 is substituted by 4,4'-oxalylbis(azanediyl)dibenzoic acid (H2ODA) and 4,4'-teraphthaloylbis(azanediyl)dibenzoic acid (H2TDA) containing amide groups (-CO-NH- motif). Furthermore, MgO6 octahedral chains where dimethyl sulfoxide (DMSO) decorating the axial position bridged two Mg2+ ions are considered. The formation energies indicate that modified CAU-8 is thermodynamically stable. The reaction mechanisms between the metal clusters and the linkers to form the materials are also proposed. GCMC calculations show that CO2 adsorptions and selectivities of Al-based MOFs are better than those of Mg-based MOFs, which is due to DMSO. Amide groups made CO2 molecules more intensively distributed besides organic linkers. CO2 uptakes and selectivities of MOFs containing H2TDA linkers are better in comparison with those of MOFs containing H2BPDC linkers or H2ODA linkers.

Chemical short-range order in derivative Cr-Ta-Ti-V-W high entropy alloys from the first-principles thermodynamic study.

The development of high-entropy alloys (HEAs) focuses on exploring compositional regions in multi-component systems with all alloy elements in equal or near-equal atomic concentrations. Initially it was based on the main idea that high mixing configurational entropy contributions to the alloy free energy could promote the formation of a single solid solution phase. By using the ab-initio based Cluster Expansion (CE) Hamiltonian model constructed for the quinary bcc Cr-Ta-Ti-V-W system in combination with Monte Carlo (MC) simulations, we show that the phase stability and chemical short-range order (SRO) of the equiatomic quinary and five sub-quaternary systems, as well as their derivative alloys, can dramatically change the order-disorder transition temperatures (ODTT) as a function of alloy compositions. In particular, it has been found, that the equiatomic quaternary Ta-Ti-V-W and Cr-Ta-Ti-W alloys had the lowest order-disorder transition temperature (500 K) among all the analysed equiatomic compositions. In all investigated alloy systems, the strongest chemical ordering has been observed between Cr and V, which led to the conclusion that decreasing the concentration of either Cr or V might be beneficial in terms of decreasing the ODTT. It also predicts that increasing concentration of Ti significantly decreases the ODTT. Our analysis of chemical SRO as a function of alloy composition allows to understand the microstructure evolution of HEAs as a function of temperature in excellent agreement with available experimental observations. Importantly, our free energy of mixing and SRO calculations predict that the origin of precipitates formed by Cr- and V-rich in the sub-quaternary Cr-Ta-V-W system is driven by the thermodynamics. The modelling results are in an excellent agreement with experimental observation of Cr and V segregation in the W0.38Ta0.36Cr0.15V0.11 alloy which in turns shows an exceptional radiation resistance.

Quantum de-trapping and transport of heavy defects in tungsten.

The diffusion of defects in crystalline materials1 controls macroscopic behaviour of a wide range of processes, including alloying, precipitation, phase transformation and creep2. In real materials, intrinsic defects are unavoidably bound to static trapping centres such as impurity atoms, meaning that their diffusion is dominated by de-trapping processes. It is generally believed that de-trapping occurs only by thermal activation. Here, we report the direct observation of the quantum de-trapping of defects below around one-third of the Debye temperature. We successfully monitored the de-trapping and migration of self-interstitial atom clusters, strongly trapped by impurity atoms in tungsten, by triggering de-trapping out of equilibrium at cryogenic temperatures, using high-energy electron irradiation and in situ transmission electron microscopy. The quantum-assisted de-trapping leads to low-temperature diffusion rates orders of magnitude higher than a naive classical estimate suggests. Our analysis shows that this phenomenon is generic to any crystalline material.

Mechano-chemical stability and water effect on gas selectivity in mixed-metal zeolitic imidazolate frameworks: a systematic investigation from van der Waals corrected density functional theory.

A series of Zn/Cu Zeolitic Imidazolate Frameworks (ZIFs) ZIF-202, -203, and -204 are systematically investigated by Density Functional Theory (DFT) with and without van der Waals (vdW) corrections. The elastic constants for non-solvent structures indicate that ZIF-202 and -204 are mechanically stable while ZIF-203 is unstable, which arises from the stiffness along the x-axis under a uniaxial strain in the PBE-D3 method. By considering the presence of solvents in ZIF-203, a structural phase transformation from a monoclinic to a triclinic structure is found which could be explained by the Jahn-Teller distortion. From the chemical bonding point of view, it is found that vdW interactions and hybridization between d-orbitals (copper) and p-orbitals (imidazolate) are the main-driving forces in stabilizing ZIF-202 and -204, respectively. The electronic structure calculations predict the presence of two optical transitions in the visible region in agreement with the experimental observation for ZIF-204 both without and with water. The DFT simulations reveal that CO2 molecules prefer to locate near imidazolate and water in dry and hydrated ZIF-204, respectively. The analysis of Canonical Monte Carlo (GCMC) simulations reveals that Coulomb interaction between CO2 and H2O molecules is mainly responsible for the enhanced CO2 uptake and selectivity under humid conditions compared to dry ones.

The electronic structures and magnetic properties of mixed-valence Fe-based metal-organic VNU-15 frameworks: a theoretical study from linear response DFT+U calculations.

The crystal symmetries, electronic structures, and magnetic properties of metal-organic VNU-15 frameworks (VNU = Vietnam National University) were investigated using density functional calculations (DFT) with an on-site Coulomb repulsion approximation, U eff, of 4.30 eV, determined via the linear response method. Two different orientations of dimethylammonium (DMA+) cations in VNU-15 were investigated. Antiferromagnetic configurations were predicted to be the ground states, with Fe ions in high-spin states for both phases. Furthermore, VNU-15 had intrinsic semiconductor electronic behavior with a small band gap of about 1.20 eV. The change in the orientation of DMA+ led to changes in the dispersion of the band structure, the band gap, and the Fe contributions to the valence band and conduction band. A fascinating feature was found involving exchange of oxidation numbers between two adjacent Fe atoms in the two phases. Our results revealed that VNU-15 has strong oxidation activity and predicted the important role of an anisotropic effect on the hole and electron effective masses. The findings presented that the electronic and magnetic properties could be controlled via hydrogen bonds and proved VNU-15 to be a prospective material for photocatalytic applications.

Hydrogen adsorption mechanism of MOF-74 metal-organic frameworks: an insight from first principles calculations.

The microscopic mechanism of the H2 adsorption of two Mg-MOF-74 isoreticular frameworks, one with a benzenedicarboxylate (BDC) linker and the other with a dihydroxyfumarate (DHF) linker, were studied on the basis of density functional theory (DFT) method. Possible adsorption sites on the internal surface of the two MOFs were detected using ab initio molecular dynamics (AIMD) annealing simulations. The simulations were able to reproduce all adsorption sites which have been experimentally observed for the BDC-based M-MOF-74 frameworks with M = Ni and Zn. In descending order of binding strengths, they are the adsorption sites primarily induced by the open metal sites P1, the oxygen atoms of the oxido groups P2 and the aromatic rings P3. The H2-framework binding strengths were properly evaluated by taking into account the vibrational zero-point energy (ZPE) contribution. An additional type of adsorption sites induced by the oxygen atoms of the carboxyl groups P4 is predicted for the Mg-MOF-74 framework. Two types of adsorption sites primarily induced by the open metal sites P1 and oxygen atoms of the carboxyl groups P2 were predicted for the DHF-based Mg-MOF-74 framework. Detailed analysis of the electron density showed that the electrostatic interaction of the H2 molecule with the charge distribution of the local framework environment within a radius of ∼3.5 Šis a key factor to define adsorption positions and binding strength. The absence of the P4 sites in the BDC-based Zn-MOF-74 framework is caused by the lower charge density at the oxygen atoms induced by less electro-positive metal. The substitution of the nonaromatic DHF linker for the aromatic BDC linker reduces the binding strength at the metal induced adsorption sites by 1.45 kJ mol-1 due to the absence of the aromatic ring.

Development of artificial intelligence models for the prediction of Compression Coefficient of soil: An application of Monte Carlo sensitivity analysis.

In this study, we developed Different Artificial Intelligence (AI) models namely Artificial Neural Network (ANN), Adaptive Network based Fuzzy Inference System (ANFIS) and Support Vector Machine (SVM) for the prediction of Compression Coefficient of soil (Cc) which is one of the most important geotechnical parameters. A Monte Carlo approach was used for the sensitivity analysis of the AI models and input parameters. For the construction and validation of the models, 189 soft clayey soil samples were analyzed. In the models study, 13 input parameters: depth of sample, bulk density, plasticity index, moisture content, clay content, specific gravity, void ratio, liquid limit, dry density, porosity, plastic limit, degree of saturation, and liquidity index were used to obtain one output parameter "Cc". Validation of the models was done using statistical methods such as Mean Absolute Error (MAE), Root Mean Square Error (RMSE), and Coefficient of determination (R2). Results of the model validation indicate that though performance of all the three models is good but SVM model is the best in the prediction of Cc. The Monte Carlo method based sensitivity analysis results show that out of the 13 input parameters considered for the models study, four parameters namely clay, degree of saturation, specific gravity and depth of sample are the most relevant in the prediction of Cc, and other parameters (bulk density, dry density, void ratio and porosity) are the most insignificant parameters for the prediction of Cc. Removal of these insignificant parameters helped to reduce the dimension of the input space and also model running time, and improved significantly the performance of the AI models. The results of this study might help in selecting the suitable AI models and input parameters for better and quick prediction of the Cc of soil.

Electron delocalization in single-layer phthalocyanine-based covalent organic frameworks: a first principle study.

In this work, we first investigate the localized electronic states in the band structures of three single-layer COFs based on typical building units of COFs chemistry. Our results confirm that the polar nature of strong bonds in these building units is a hindrance to a fully delocalized structure and disfavors the band-like mechanism of transport. We then show that a rational design of the building units can lead to dispersive band states in the electronic structure and results in conducting single-layer COFs. We demonstrate this strategy by investigating the charge carrier transport in a series of single-layer Ni-phthalocyanine (NiPc) covalent organic frameworks (COFs), namely, NiPc-P, NiPc-2P, and NiPc-3P. Three proposed COFs exhibit semiconducting band gaps ranging from 0.55 to 0.91 eV. Their room-temperature intrinsic mobility is predicted to be in range of 200-600 cm2 V-1 s-1 and 20 000-60 000 cm2 V-1 s-1 for electrons and holes, respectively, which are comparable to those of phosphorene and higher than those of the trigonal prismatic molybdenum disulfide. NiPc are dynamically and mechanically stable and can be synthesized via the co-evaporation between Ni and corresponding tetracyano linkers. Importantly, we demonstrate that the properties of the single-layer COFs can be tuned by engineering the organic building blocks. Our theoretical study not only provides insight into the design principles for semiconducting single-layer COFs but also highlights the significance of reticular chemistry in the development of a new generation of two-dimensional materials for optoelectronic applications.

Configurational Entropy in Multicomponent Alloys: Matrix Formulation from Ab Initio Based Hamiltonian and Application to the FCC Cr-Fe-Mn-Ni System.

Configuration entropy is believed to stabilize disordered solid solution phases in multicomponent systems at elevated temperatures over intermetallic compounds by lowering the Gibbs free energy. Traditionally, the increment of configuration entropy with temperature was computed by time-consuming thermodynamic integration methods. In this work, a new formalism based on a hybrid combination of the Cluster Expansion (CE) Hamiltonian and Monte Carlo simulations is developed to predict the configuration entropy as a function of temperature from multi-body cluster probability in a multi-component system with arbitrary average composition. The multi-body probabilities are worked out by explicit inversion and direct product of a matrix formulation within orthonomal sets of point functions in the clusters obtained from symmetry independent correlation functions. The matrix quantities are determined from semi canonical Monte Carlo simulations with Effective Cluster Interactions (ECIs) derived from Density Functional Theory (DFT) calculations. The formalism is applied to analyze the 4-body cluster probabilities for the quaternary system Cr-Fe-Mn-Ni as a function of temperature and alloy concentration. It is shown that, for two specific compositions (Cr 25Fe 25Mn 25Ni 25 and Cr 18Fe 27Mn 27Ni 28), the high value of probabilities for Cr-Fe-Fe-Fe and Mn-Mn-Ni-Ni are strongly correlated with the presence of the ordered phases L1 2 -CrFe 3 and L1 0-MnNi, respectively. These results are in an excellent agreement with predictions of these ground state structures by ab initio calculations. The general formalism is used to investigate the configuration entropy as a function of temperature and for 285 different alloy compositions. It is found that our matrix formulation of cluster probabilities provides an efficient tool to compute configuration entropy in multi-component alloys in a comparison with the result obtained by the thermodynamic integration method. At high temperatures, it is shown that many-body cluster correlations still play an important role in understanding the configuration entropy before reaching the solid solution limit of high-entroy alloys (HEAs).

Monitoring Mechanical, Electronic, and Catalytic Trends in a Titanium Metal Organic Framework Under the Influence of Guest-Molecule Encapsulation Using Density Functional Theory.

In this study, we conduct a density functional theory investigation to study the mechanical stability of a titanium-based metal organic framework (MOF-901), which was hypothetically assumed to possess 2D characteristics. It is systematically found that the encapsulation of methanol enhances the mechanical stability of MOF-901 as the elastic tensors Cij of MOF-901∙nMeOH are higher than the corresponding Cij quantities reported for solvent-free MOF-901. Moreover, the 2D characteristics of MOF-901 is confirmed by verifying the negative values of C33. At the same time, the band gap of MOF-901 is observed to be solvent-dependent. In its pure form, MOF-901 possesses a direct gap (Eg) of 2.07 eV, with the valence and conduction bands mainly constituted by electrons of 4-aminobenzoate linkers. Introducing methanol into MOF-901 causes distortion to the 4-aminobenzoate geometry, thereby induces electronic degeneracy to the conduction bands. Consequently, Eg is narrowed to 1.84 eV with 5.7 wt% MeOH or 1.63 eV with 11.4 wt% MeOH. Hence, it is possible to tailor the band gap of MOF-901 by controlling methanol guest, which only acquires van der Waals interaction to the framework. In addition, our theoretical prediction shows a Ti(IV) site can undergo electronic hopping to become Ti(III) under the effect of visible light (~440-443 nm). Then, Ti(III) is capable of breaking the C-Br bond in ethyl α-bromophenylacetate spontaneously, which in turn activates the polymerization of methyl methacrylate with an energy barrier of 0.30 eV.

The Effect of Electronic Structure on the Phases Present in High Entropy Alloys.

Multicomponent systems, termed High Entropy Alloys (HEAs), with predominantly single solid solution phases are a current area of focus in alloy development. Although different empirical rules have been introduced to understand phase formation and determine what the dominant phases may be in these systems, experimental investigation has revealed that in many cases their structure is not a single solid solution phase, and that the rules may not accurately distinguish the stability of the phase boundaries. Here, a combined modelling and experimental approach that looks into the electronic structure is proposed to improve accuracy of the predictions of the majority phase. To do this, the Rigid Band model is generalised for magnetic systems in prediction of the majority phase most likely to be found. Good agreement is found when the predictions are confronted with data from experiments, including a new magnetic HEA system (CoFeNiV). This also includes predicting the structural transition with varying levels of constituent elements, as a function of the valence electron concentration, n, obtained from the integrated spin-polarised density of states. This method is suitable as a new predictive technique to identify compositions for further screening, in particular for magnetic HEAs.

First-principles modeling of 3d-transition-metal-atom adsorption on silicene: a linear-response DFT + U approach.

By employing DFT + U calculations with the linear response method, we investigate the interactions between various 3d transition-metal atoms (Cr, Mn, Fe, Co) and silicene. In the cases of two-dimensional (2D) FeSi2 and CoSi2, the metal atoms tend to penetrate into the silicene layer. While CoSi2 is non-magnetic, FeSi2 exhibits a total magnetic moment of 2.21 µ(B)/cell. Upon the examination of 2D MSi6, a trend in anti-ferromagnetic (AFM) favorability in the z-direction is observed according to our DFT + U calculations. In the ferromagnetic (FM) states (less stable), each primary unit cell of CrSi6, MnSi6, and FeSi6 possesses different levels of total magnetization (4.01, 5.18, and 2.00 µ B/cell, respectively). The absolute magnetization given by AFM MSi6 structures varies in the range of 5.33-5.84 µ(B)/cell. A direct band gap in AFM MnSi6 (0.2 eV) is predicted, while the metastable FM FeSi6 structure has a wider band gap (0.85 eV). Interestingly, there are superexchange interactions between metal atoms in the MSi6 systems, which result in the AFM alignments.

First-principles modeling of C60-Cr-graphene nanostructures for supporting metal clusters.

We present a first-principles modeling study of a new class of nanomaterials in which buckminsterfullerene (C60) and graphene (G) are bridged by Cr via coordination bonds. Two nanostructures denoted as G(C54)-Cr-C60 and G(C150)-Cr-C60 are investigated, which share many similarities in the configuration geometries but differ in the distribution densities of Cr-C60 on the graphene surface. The binding energies between C60 and the rest of the system in these complexes are calculated to be 2.59 and 2.10 eV, respectively, indicative of their good structural stability. Additional spin-polarized calculations indicate that G(C54)-Cr-C60 is weakly ferromagnetic, which is chiefly due to the contribution from the 3d shell of Cr. We then investigate three model complexes of C60-Cr-G(C54) and a metal cluster (Ni4, Pd4, or Pt4). The binding energies of these three nanostructures are significantly large (3.57, 2.38, and 4.35 eV, respectively). Electron density analysis along the Ni-C, Pd-C, and Pt-C bonds consistently affirms that the Pt-C bond is the strongest while the Pd-C bond is the weakest. The strong Pt-C bond is attributed to the effective overlap of 5d(z(2)) (Pt) and 2p(z) (C) orbitals. Partial density of states analysis indicates that Ni4 and Pd4 substantially contribute to the strong ferromagnetism of the complexes, whereas Pt4 is observed to be non-magnetic even when the spin-orbit coupling is taken into account. H2 dissociation on the Ni4 complex is also examined, and the estimated reaction barrier is relatively low (0.76 eV).

Anatase-rutile phase transformation of titanium dioxide bulk material: a DFT + U approach.

The anatase-rutile phase transformation of TiO(2) bulk material is investigated using a density functional theory (DFT) approach in this study. According to the calculations employing the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the Vanderbilt ultrasoft pseudopotential, it is suggested that the anatase phase is more energetically stable than rutile, which is in variance with the experimental observations. Consequently, the DFT + U method is employed in order to predict the correct structural stability in titania from electronic-structure-based total energy calculations. The Hubbard U term is determined by examining the band structure of rutile with various values of U from 3 to 10 eV. At U = 5 eV, a theoretical bandgap for rutile is obtained as 3.12 eV, which is in very good agreement with the reported experimental bandgap. Hence, we choose the DFT + U method (with U = 5 eV) to investigate the transformation pathway using the newly-developed solid-state nudged elastic band (ss-NEB) method, and consequently obtain an intermediate transition structure that is 9.794 eV per four-TiO(2) above the anatase phase. When the Ti-O bonds in the transition state are examined using charge density analysis, seven Ti-O bonds (out of 24 bonds in the anatase unit cell) are broken, and this result is in excellent agreement with a previous experimental study (Penn and Banfield 1999 Am. Miner. 84 871-6).