Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

We study the low-pressure (0 to 10 GPa) phase diagram of crystalline benzene using quantum Monte Carlo (QMC) and density functional theory (DFT) methods. We consider the $Pbca$, $P4_32_12$, and $P2_1/c$ structures as the best candidates for phase I and phase II. We perform diffusion quantum Monte Carlo (DMC) calculations to obtain accurate static phase diagrams as benchmarks for modern van der Waals density functionals. We use density functional perturbation theory to compute phonon contribution in the free-energy calculations. Our DFT enthalpy-pressure phase diagram indicates that the $Pbca$ and $P2_1/c$ structures are the most stable phases within the studied pressure range. The DMC Gibbs free-energy calculations predict that the room temperature $Pbca$ to $P2_1/c$ phase transition occurs at 2.1(1) GPa. This prediction is consistent with available experimental results at room temperature. Our DMC calculations show an estimate of 50.6$\pm$0.5 kJ/mol for crystalline benzene lattice energy

Chemical accuracy from quantum Monte Carlo for the Benzene Dimer

We report an accurate study of interactions between Benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory (DFT) using different van der Waals (vdW) functionals. In our QMC calculations, we use accurate correlated trial wave functions including three-body Jastrow factors, and backflow transformations. We consider two benzene molecules in the parallel displaced (PD) geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of -2.3(4) and -2.7(3) kcal/mol, respectively. The best estimate of the CCSD(T)/CBS limit is -2.65(2) kcal/mol [E. Miliordos et al, J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.Comment: Accepted for publication in the Journal of Chemical Physics, Vol. 143, Issue 11, 201

Dissociation of high-pressure solid molecular hydrogen: Quantum Monte Carlo and anharmonic vibrational study

A theoretical study is reported of the molecular-to-atomic transition in solid hydrogen at high pressure. We use the diffusion quantum Monte Carlo method to calculate the static lattice energies of the competing phases and a density-functional-theory-based vibrational self-consistent field method to calculate anharmonic vibrational properties. We find a small but significant contribution to the vibrational energy from anharmonicity. A transition from the molecular Cmca-12 direct to the atomic I4_1/amd phase is found at 374 GPa. The vibrational contribution lowers the transition pressure by 91 GPa. The dissociation pressure is not very sensitive to the isotopic composition. Our results suggest that quantum melting occurs at finite temperature.Comment: Accepted for publication by Phys. Rev. Let

A social perspective on soil functions and quality improvement : Romanian farmers’ perceptions

Agriculture is a key player in the conservation of natural resources and cultural landscapes and one of the most prominent interfaces between human activity and soil. The present paper reveals a social perspective on soil functions. In this context, it was assumed that perceptions of soil functions could transform themselves into components of agro-ecosystems and influence the whole decision-making process. Therefore, it is indispensable to look at farmers when approaching soil functions. The objective of this study was twofold. Firstly, Romanian farmers' perception of the importance of soil functions was investigated. Secondly, it was revealed how well farmers' perception of soil functions importance and socio-economic variables could predict the "Use of compost". Soil functions were selected based on an extensive literature review. Farmers' perceptions of soil functions and the use of compost as a measure taken to improve soil productivity were studied through a questionnaire applied to a sample of 278 Romanian farmers randomly selected from sixteen villages. Binary logistic regression revealed that the perceived importance of two soil functions could predict the use of compost - "Water quantity regulation" and "Water quality maintenance and enhancement". The study concluded that strengthening the importance of the "Water quantity regulation" function in farmers' minds can stimulate the use of compost. It was also inferred that because younger farmers are more prone to composting, they will be more receptive to marketing actions related to compost use, such as the acquisitions of materials and instruments useful for compost production and use. In a context where a real dialogue to elaborate well-grounded environmental policies is still elusive because of differences between farmers and policy-makers' views, investigation of farmers' perceptions can bring a significant contribution towards a bottom-up approach for sustainable soil management

Defects in Crystalline Packings of Twisted Filament Bundles: II. Dislocations and Grain Boundaries

Twisted and rope-like assemblies of filamentous molecules are common and vital structural elements in cells and tissue of living organisms. We study the intrinsic frustration occurring in these materials between the two-dimensional organization of filaments in cross section and out-of-plane interfilament twist in bundles. Using non-linear continuum elasticity theory of columnar materials, we study the favorable coupling of twist-induced stresses to the presence of edge dislocations in the lattice packing of bundles, which leads to a restructuring of the ground-state order of these materials at intermediate twist. The stability of dislocations increases as both the degree of twist and lateral bundle size grow. We show that in ground states of large bundles, multiple dislocations pile up into linear arrays, radial grain boundaries, whose number and length grows with bundle twist, giving rise to a rich class of "polycrystalline" packings.Comment: 10 pages, 7 figure

A qualitative study of the infant feeding beliefs and behaviours of mothers with low educational attainment

© 2016 Russell et al. Background: Infancy is an important period for the promotion of healthy eating, diet and weight. However little is known about how best to engage caregivers of infants in healthy eating programs. This is particularly true for caregivers, infants and children from socioeconomically disadvantaged backgrounds who experience greater rates of overweight and obesity yet are more challenging to reach in health programs. Behaviour change interventions targeting parent-infant feeding interactions are more likely to be effective if assumptions about what needs to change for the target behaviours to occur are identified. As such we explored the precursors of key obesity promoting infant feeding practices in mothers with low educational attainment. Methods: One-on-one semi-structured telephone interviews were developed around the Capability Opportunity Motivation Behaviour (COM-B) framework and applied to parental feeding practices associated with infant excess or healthy weight gain. The target behaviours and their competing alternatives were (a) initiating breastfeeding/formula feeding, (b) prolonging breastfeeding/replacing breast milk with formula, (c) best practice formula preparation/sub-optimal formula preparation, (d) delaying the introduction of solid foods until around six months of age/introducing solids earlier than four months of age, and (e) introducing healthy first foods/introducing unhealthy first foods, and (f) feeding to appetite/use of non-nutritive (i.e., feeding for reasons other than hunger) feeding. The participants' education level was used as the indicator of socioeconomic disadvantage. Two researchers independently undertook thematic analysis. Results: Participants were 29 mothers of infants aged 2-11 months. The COM-B elements of Social and Environmental Opportunity, Psychological Capability, and Reflective Motivation were the key elements identified as determinants of a mother's likelihood to adopt the healthy target behaviours although the relative importance of each of the COM-B factors varied with each of the target feeding behaviours. Conclusions: Interventions targeting healthy infant feeding practices should be tailored to the unique factors that may influence mothers' various feeding practices, taking into account motivational and social influences

The image of nursing, as perceived by Iranian male nurses

The stereotypical public image of nursing is a major concern for male nurses around the world. In this study, we explored how Iranian male nurses perceived the public view of nurses, and their perceptions of themselves. A qualitative descriptive design and content analysis were used to obtain data from 18 purposely-selected male hospital nurses with a baccalaureate nursing degree in Tabriz, Iran. Semistructured interviews were conducted and analyzed. Two main themes emerged: (i) the outsider's view of nursing, which referred to the participants' perceptions of their public image; and (ii) the insider's view, which related to the male nurses' perceptions of themselves. Results included personal transition into a positive professional self-image through the educational process, and continued public perception of nursing as a female profession ill-suited for a man. Strategies to improve the insider's and outsider's views of nursing are listed to help recruit and retain more Iranian male nurses