Effects of cognitive-motor intervention for pediatric posterior fossa tumor survivors: results of a pilot study.

The purpose of this prospective pilot study was to evaluate the feasibility and effects of cognitive-motor intervention on the cognitive and motor abilities of pediatric survivors of posterior fossa tumors. The study involved patients aged 7 to 18 years with cognitive deficits who had completed primary treatment for posterior fossa tumors. 25 participants (Mage=11.3 ± 2.93, 64% male; 17 medulloblastoma, 1 ependymoma, 1 desmoplastic medulloblastoma, 6 piloid astrocytoma; 22 in remission (Mmonths =45), 3 in stabilization (Mmonths=49)) were recruited from the Research Institute for Brain Development and Peak Performance. The intervention consisted of two phases with a 3-month break for home training, and a total duration of 6 months. Each phase lasted 7 weeks and included two assessment procedures (pre- and post-intervention) and 10 training sessions over a period of 5 weeks (two 3-hour sessions per week). At baseline and pre- and post-intervention, all participants underwent a battery of cognitive and motor tests. Each training session included gross motor training (GMT), graphomotor training (GT), and cognitive-motor training (CMT). Statistical analysis was performed using the Friedman test for repeated measures and post-hoc Durbin-Conover test. The results indicated significant improvements in visuospatial working memory, visual attention, eye-hand coordination, semantic verbal fluency, auditory-motor synchronization, reaction time, and a decrease in the rate of ataxia. These improvements remained stable even in the absence of direct intervention. The findings demonstrate positive effects and feasibility of the intervention and suggest the need for further research in this area including randomized controlled feasibility studies with a larger sample.

Superoxide-producing associates from gastrointestinal bacteria: stimulation of its growth by exogenous superoxide-producing complex from raspberries.

Aerobic organisms including the gut microbiota have an essential antioxidant status, as a result of which these bacteria protect organisms from various pathologies and diseases. The goal of the given investigation is (1) the isolation and purification of the isoforms of endogenous О2--producing associate from gastrointestinal bacteria (Lactobacillus rhamnosus, Lactobacillus acidophilus, Bifidobacterium bifidum); (2) determination of the effective concentrations of exogenous О2- produced by a complex of NADPH-containing protein component and Fe(III) (NPC-Fe(III)) from raspberries on the growth of the gastrointestinal bacteria in a nutrient medium in vitro. Ion-exchange chromatography on cellulose DE-52 and gel filtration on Sephadex G-100 at the pH of 9.5 was used to isolate and purify the NLP-Nox isoforms. Specific maximal optical absorption spectra of the Nox isoforms were observed in a weakly opalescent aqueous solution of the NLP-Nox isoforms. The specific contents of these NLP-Nox isoforms, as well as their composition, the stationary concentration of produced О2-, and the mechanism of О2- production were determined. The stimulating effect on the growth of these gastrointestinal bacteria in the nutrient medium of MRS broth and MRS agar in vitro under the influence of О2-, as a product of a new thermostable and acid-stable complex NPC-Fe(III) was determined. The NPC-Fe(III) complex, from raspberries was determined as well. Thus, for the first time, the isolation and purification of О2-- producing thermostable NADPH-containing lipoprotein-NADPH oxidase (NLP-Nox) associate from gastrointestinal bacteria membranes (continuously producing О2- under the aerobic conditions), and the stimulation of these bacteria growth by О2- formed by the complex from raspberries were demonstrated.

The О₂⁻-producing associate NLP-Nox was isolated and purified from the gut microbiota.NLP-Nox associate produces О₂⁻ by using a protein-bound non-free NADPH as a substrate.The NPC-Fe(III) isolated from raspberries generates О₂⁻.The effective quantities of О₂⁻ promotes the growth and development of bacteria.

A Practical Approach to Left Main Coronary Artery Disease: JACC State-of-the-Art Review.

The treatment of left main (LM) coronary artery disease (CAD) requires complex decision-making. Recent clinical practice guidelines provide clinicians with guidance; however, decisions regarding treatment for individual patients can still be difficult. The American College of Cardiology's Cardiac Surgery Team and Interventional Council joined together to develop a practical approach to the treatment of LM CAD, taking into account randomized clinical trial, meta-analyses, and clinical practice guidelines. The various presentations of LM CAD based on anatomy and physiology are presented. Recognizing the complexity of LM CAD, which rarely presents isolated and is often in combination with multivessel disease, a treatment algorithm with medical therapy alone or in conjunction with percutaneous coronary intervention or coronary artery bypass grafting is proposed. A heart team approach is recommended that accounts for clinical, procedural, operator, and institutional factors, and features shared decision-making that meets the needs and preferences of each patient and their specific clinical situation.

Phase stability and dense polymorph of the BaCa(CO3)2 barytocalcite carbonate.

The double carbonate BaCa(CO3)2 holds potential as host compound for carbon in the Earth's crust and mantle. Here, we report the crystal structure determination of a high-pressure BaCa(CO3)2 phase characterized by single-crystal X-ray diffraction. This phase, named post-barytocalcite, was obtained at 5.7 GPa and can be described by a monoclinic Pm space group. The barytocalcite to post-baritocalcite phase transition involves a significant discontinuous 1.4% decrease of the unit-cell volume, and the increase of the coordination number of 1/4 and 1/2 of the Ba and Ca atoms, respectively. High-pressure powder X-ray diffraction measurements at room- and high-temperatures using synchrotron radiation and DFT calculations yield the thermal expansion of barytocalcite and, together with single-crystal data, the compressibility and anisotropy of both the low- and high-pressure phases. The calculated enthalpy differences between different BaCa(CO3)2 polymorphs confirm that barytocalcite is the thermodynamically stable phase at ambient conditions and that it undergoes the phase transition to the experimentally observed post-barytocalcite phase. The double carbonate is significantly less stable than a mixture of the CaCO3 and BaCO3 end-members above 10 GPa. The experimental observation of the high-pressure phase up to 15 GPa and 300 ºC suggests that the decomposition into its single carbonate components is kinetically hindered.

Structural, vibrational and electronic properties of α'-Ga2S3 under compression.

We report a joint experimental and theoretical study of the low-pressure phase of α'-Ga2S3 under compression. Theoretical ab initio calculations have been compared to X-ray diffraction and Raman scattering measurements under high pressure carried out up to 17.5 and 16.1 GPa, respectively. In addition, we report Raman scattering measurements of α'-Ga2S3 at high temperature that have allowed us to study its anharmonic properties. To understand better the compression of this compound, we have evaluated the topological properties of the electron density, the electron localization function, and the electronic properties as a function of pressure. As a result, we shed light on the role of the Ga-S bonds, the van der Waals interactions inside the channels of the crystalline structure, and the single and double lone electron pairs of the sulphur atoms in the anisotropic compression of α'-Ga2S3. We found that the structural channels are responsible for the anisotropic properties of α'-Ga2S3 and the A'(6) phonon, known as the breathing mode and associated with these channels, exhibits the highest anharmonic behaviour. Finally, we report calculations of the electronic band structure of α'-Ga2S3 at different pressures and find a nonlinear pressure behaviour of the direct band gap and a pressure-induced direct-to-indirect band gap crossover that is similar to the behaviour previously reported in other ordered-vacancy compounds, including ß-Ga2Se3. The importance of the single and, more specially, the double lone electron pairs of sulphur in the pressure dependence of the topmost valence band of α'-Ga2S3 is stressed.

Controlling the off-center positions of anions through thermodynamics and kinetics in flexible perovskite-like materials.

Due to the network flexibility of their BX3 sub-lattice, a manifold of polymorphs with potential multiferroic applications can be found in perovskite-like ABX3 materials under different pressure and temperature conditions. The potential energy surface of these compounds usually presents equivalent off-center positions of anions connected by low energetic barriers. This feature facilitates a competition between the thermodynamic and kinetic control of the transitions from low to high symmetry structures, and explains the relationship between the rich polymorphism and network flexibility. In the rhombohedral phase of iron trifluoride, our first-principles electronic structure and phonon calculations reveal the factors that determine which of the two scenarios dominates the transition. At the experimentally reported rhombohedral-cubic transition temperature, the calculated fluorine displacements are fast enough to overcome forward and backward a barrier of less than 30 kJ mol-1, leading to an average structure with cubic symmetry. In addition, lattice strain effects observed in epitaxial growth and nanocrystallite experiments involving BX3 compounds are successfully mimicked by computing the phase stability of FeF3 under negative pressures. We predict a transition pressure at -1.8 GPa with a relative volume change around 5%, consistent with a first-order transition from the rhombohedral to the cubic structure. Overall, our study illustrates how, by strain tuning, either a thermodynamic or a kinetic pathway can be selected for this transformation.

Temperature and pressure-induced strains in anhydrous iron trifluoride polymorphs.

Various structural configurations of iron trifluoride appear at the nanoscale and macroscopic size, either in the amorphous or crystalline state. The specific atomic organization in these structures crucially alters the performance of FeF3 as an effective cathode in Li-ion batteries. Our detailed first-principles computational simulations examine the structural strains induced by temperature and stress on the four anhydrous polymorphs observed so far in FeF3 at ambient pressure. A wealth of data covering previous experimental results on their equilibrium structures and extending their characterization with new static and isothermal equations of state is provided. We inform on how porous apertures associated with the six-octahedra rings of the HTB and pyrochlore phases are modified under compressive and expansive strains. A quasi-auxetic behavior at low pressures for the ground state rhombohedral phase is detected, which is in concordance with its anomalous structural anisotropy. In contrast with the effect of temperature, this structure undergoes under negative pressure phase transitions to the other three polymorphs, indicating potential conditions where low-density FeF3 could show a better performance in technological applications.

Perinatal and early-life cobalt exposure impairs essential metal metabolism in immature ICR mice.

The objective of the present study was to assess the impact of cobalt (Co) exposure on tissue distribution of iron (Fe), copper (Cu), manganese (Mn), and zinc (Zn), as well as serum hepcidin levels in immature mice (18, 25, 30 days). Pregnant mice were exposed to 75 mg/kg b.w. cobalt chloride (CoCl2 × 6H2O) with drinking water starting from 3 days before delivery and during lactation. At weaning (day 25) the offspring were separated and housed in individual cages with subsequent exposure to 75 mg/kg b.w. CoCl2 until 30 days postnatally. Evaluation of tissue metal levels was performed by an inductively coupled plasma-mass spectrometry (ICP-MS). Serum hepcidin level was assayed by enzyme linked immunosorbent assay (ELISA). Cobalt exposure resulted in a time- and tissue-dependent increase in Co levels in kidney, spleen, liver, muscle, erythrocytes, and serum on days 18, 25, and 30. In parallel with increasing Co levels, CoCl2 exposure resulted in a significant accumulation of Cu, Fe, Mn, and Zn in the studied tissues, with the effect being most pronounced in 25-day-old mice. Cobalt exposure significantly increased serum hepcidin levels only in day18 mice. The obtained data demonstrate that Co exposure may alter essential metal metabolism in vivo.

Oral pigmented lesions: a retrospective analysis from Brazil.

BACKGROUND: Pigmented lesions are uncommon in the oral mucosa, and studies investigating the incidence and types of these lesions are desired to improve the diagnostic knowledge of clinicians. The aim of this study was to analyze the distribution of oral pigmented lesions in a Brazilian population. MATERIAL AND METHODS: A retrospective descriptive cross-sectional study was performed. Oral pigmented lesions were retrieved from the files of two oral and maxillofacial pathology services from Brazil over a 45-year period (1974-2019). The clinical data and the diagnoses of each case were retrieved and included in a Microsoft Excel® database. RESULTS: From 77.074 lesions diagnosed in this period, 761 (0.99%) represented pigmented lesions of the oral mucosa, including 351 (46.1%) melanocytic and 410 (53.9%) non-melanocytic lesions, with a higher incidence in females (73.2%) between the fourth and seventh decades of life. Amalgam tattoo (53.6%) represented the most common lesion, followed by melanotic macule (18.3%) and racial pigmentation (10.8%). Other pigmented lesions included nevus (9.9%), post-inflammatory pigmentation (3%), melanoma (2.1%), melanoacanthoma (1.4%), smoker's melanosis (0.4%), drug-induced pigmentation (0.3%), and melanotic neuroectodermal tumor of infancy (0.1%). The buccal mucosa was the most commonly affected site (25.2%), followed by the alveolar ridge (14.5%), and gingiva (11.8%). CONCLUSIONS: The current findings were similar to previous studies with minor differences due methodology and characteristics of the services from where lesions were retrieved. The knowledge of these data may contribute to a better understanding of oral pigmented lesions and assist clinicians to better recognize and manage them.

Application of XDM to ionic solids: The importance of dispersion for bulk moduli and crystal geometries.

Dispersion corrections are essential in the description of intermolecular interactions; however, dispersion-corrected functionals must also be transferrable to hard solids. The exchange-hole dipole moment (XDM) model has demonstrated excellent performance for non-covalent interactions. In this article, we examine its ability to describe the relative stability, geometry, and compressibility of simple ionic solids. For the specific cases of the cesium halides, XDM-corrected functionals correctly predict the energy ranking of the B1 and B2 forms, and a dispersion contribution is required to obtain this result. Furthermore, for the lattice constants of the 20 alkali halides, the performance of XDM-corrected functionals is excellent, provided that the base functional's exchange enhancement factor properly captures non-bonded repulsion. The mean absolute errors in lattice constants obtained with B86bPBE-XDM and B86bPBE-25X-XDM are 0.060 Å and 0.039 Å, respectively, suggesting that delocalization error also plays a minor role in these systems. Finally, we considered the calculation of bulk moduli for alkali halides and alkaline-earth oxides. Previous claims in the literature that simple generalized gradient approximations, such as PBE, can reliably predict experimental bulk moduli have benefited from large error cancellations between neglecting both dispersion and vibrational effects. If vibrational effects are taken into account, dispersion-corrected functionals are quite accurate (4 GPa-5 GPa average error), again, if non-bonded repulsion is correctly represented. Careful comparisons of the calculated bulk moduli with experimental data are needed to avoid systematic biases and misleading conclusions.

Patterns of alveolar macrophage activation upon attenuated and virulent African swine fever viruses in vitro.

The pattern of porcine alveolar macrophage (AM) activation upon classical stimuli of two strains of African swine fever (ASF) viruses, an attenuated ASFV-BA71V and virulent ASFV-Georgia2007 were investigated. In an in vitro experiment ASFV-Georgia2007-infected AM showed M1 polarization pattern different from the one induced by classical stimuli. Altered morphology, appearance of binuclear cells, decreased synthesis of IFN-alpha as well as IFN-epsilon was observed compared with attenuated ASFV-BA71V, and decreased synthesis of IFN-omega compared with intact cells. However, CD68 level did not significantly differ between alveolar macrophage populations infected by ASFV-Georgia2007 and control group, while both LPS/IFN-gamma stimulation and non-pathogenic ASFV-BA71V virus increased the level of CD68 soluble receptor. AM infection with ASFV-Georgia2007 resulted in remarkable DNA proliferation whereas LPS/IFN-gamma and ASFV-BA71V induced less expressed DNA proliferation in activated cells. The higher value of nitric oxide was obvious in the cells infected with ASFV-BA71V, compared to ASFV-Georgia2007 and LPS/IFN-gamma activated cells. In conclusion, pattern of activation of alveolar macrophages induced by ASFV-Georgia2007 virus differs from the one expressed in LPS/IFN-gamma- and ASFV-BA71V-activated cells. ASFV-BA71V and LPS/IFN-gamma share similar antiviral response of porcine AM. Therefore we assume that wild type virulent ASFV can partially down regulate antiviral response of AM and conclude that evolutionary decrease of virulence in ASFV is related to alterations of control of the host cell antiviral response.

Improved Basis-Set Incompleteness Potentials for Accurate Density-Functional Theory Calculations in Large Systems.

The accurate calculation of chemical properties using density-functional theory (DFT) requires the use of a nearly complete basis set. In chemical systems involving hundreds to thousands of atoms, the cost of the calculations place practical limitations on the number of basis functions that can be used. Therefore, in most practical applications of DFT to large systems, there exists a basis-set incompleteness error (BSIE). In this article, we present the next iteration of the basis-set incompleteness potentials (BSIPs), one-electron potentials designed to correct for basis-set incompleteness error. The ultimate goal associated with the development of BSIPs is to allow the calculation of molecular properties using DFT with near-complete-basis-set results at a computational cost that is similar to a small basis set calculation. In this work, we develop BSIPs for 10 atoms in the first and second rows (H, B-F, Si-Cl) and 15 common basis sets of the Pople, Dunning, Karlsruhe, and Huzinaga types. Our new BSIPs are constructed to minimize BSIE in the calculation of reaction energies, barrier heights, noncovalent binding energies, and intermolecular distances. The BSIPs were obtained using a training set of 15 944 data points. The fitting approach employed a regularized linear least-squares method with variable selection (the LASSO method), which results in a much better fit to the training data than our previous BSIPs while, at the same time, reducing the computational cost of BSIP development. The proposed BSIPs are tested on various benchmark sets and demonstrate excellent performance in practice. Our new BSIPs are also transferable; i.e., they can be used to correct BSIE in calculations that employ density functionals other than the one used in the BSIP development (B3LYP). Finally, BSIPs can be used in any quantum chemistry program that have implemented effective-core potentials without changes to the software.

What is "many-body" dispersion and should I worry about it?

Inclusion of dispersion effects in density-functional calculations is now standard practice in computational chemistry. In many dispersion models, the dispersion energy is written as a sum of pairwise atomic interactions consisting of a damped asymptotic expansion from perturbation theory. There has been much recent attention drawn to the importance of "many-body" dispersion effects, which by their name imply limitations with a pairwise atomic expansion. In this perspective, we clarify what is meant by many-body dispersion, as this term has previously referred to two very different physical phenomena, here classified as electronic and atomic many-body effects. Atomic many-body effects refer to the terms in the perturbation-theory expansion of the dispersion energy involving more than two atoms, the leading contribution being the Axilrod-Teller-Muto three-body term. Conversely, electronic many-body effects refer to changes in the dispersion coefficients of the pairwise terms induced by the atomic environment. Regardless of their nature, many-body effects cause pairwise non-additivity in the dispersion energy, such that the dispersion energy of a system does not equal the sum of the dispersion energies of its atomic pairs taken in isolation. A series of examples using the exchange-hole dipole moment (XDM) method are presented to assess the relative importance of electronic and atomic many-body effects on the dispersion energy. Electronic many-body effects can result in variation in the leading-order C6 dispersion coefficients by as much as 50%; hence, their inclusion is critical for good performance of a pairwise asymptotic dispersion correction. Conversely, atomic many-body effects represent less than 1% of the total dispersion energy and are much less significant than higher-order (C8 and C10) pairwise terms. Their importance has been previously overestimated through empirical fitting, where they can offset underlying errors stemming either from neglect of higher-order pairwise terms or from the base density functional.

Asymptotic Pairwise Dispersion Corrections Can Describe Layered Materials Accurately.

A recent study by Tawfik et al. [ Phys. Rev. Mater. 2018, 2, 034005] found that few density functionals, none of which are asymptotic pairwise dispersion methods, describe the geometry and binding of layered materials accurately. Here, we show that the exchange-hole dipole moment (XDM) dispersion model attains excellent results for graphite, hexagonal BN, and transition-metal dichalcogenides. Contrary to what has been argued, successful modeling of layered materials does not necessitate meta-GGA exchange, nonlocal correlation functionals, or the inclusion of three-body dispersion terms. Rather, a GGA functional, combined with a simple asymptotic pairwise dispersion correction, can be reliably used, provided that it properly accounts for the geometric dependence of the dispersion coefficients. The overwhelming contribution to the variation of the pairwise dispersion coefficients comes from the immediate vicinity of an atom and is already present for single layers. Longer-range and interlayer effects are examined in detail for graphite.

Serum zinc, copper, zinc-to-copper ratio, and other essential elements and minerals in children with attention deficit/hyperactivity disorder (ADHD).

BACKGROUND: Essential trace elements and minerals play a significant role in neurodevelopment. Although certain studies demonstrated impaired essential trace element and mineral status in children with ADHD, the existing data are insufficient. The objective of the present study was to assess serum trace element and mineral levels in children with ADHD. METHODS: Serum trace element and mineral levels in 68 children with ADHD and 68 neurotypical controls were assessed using ICP-MS at NexION 300D (PerkinElmer Inc., USA) equipped with ESI SC-2 DX4 autosampler (Elemental Scientific Inc., USA). RESULTS: Serum Cr, Mg, and Zn levels in children with ADHD were 21 % (p = 0.010), 4 % (p = 0.005), and 7 % (p = 0. 001) lower as compared to the healthy controls, respectively. In turn, serum Cu/Zn values were 11 % higher than those in the control group. Age and gender had a significant impact on serum element levels in ADHD. Particularly, preschool children were characterized by significantly increased Cu (+8 %; p = 0.034), and Cu/Zn (+19 %; p < 0.001) values, whereas serum Zn (-9 %; p = 0.004) level was decreased. In primary school-aged children only 6 % (p = 0.007) lower Mg levels were observed. Both boys and girls with ADHD were characterized by 8 % (p = 0.016) lower serum Zn levels and 10 % (p = 0.049) higher Cu/Zn values when compared to neurotypical girls. Boys with ADHD also had significantly higher Cu/Zn, exceeding the respective control values by 12 % (p = 0.021), predominantly due to a 7 % (p = 0.035) decrease in serum Zn. Serum Mg levels were also found to be significantly lower than those in neurotypical children by 5 % (p = 0.007). In adjusted regression models serum Cr (ß=-0.234; p = 0.009) and Cu/Zn (ß = 0.245; p = 0.029) values were significantly associated with ADHD, respectively. Two-way ANOVA revealed a significant impact of ADHD on Cr, Mg, Zn, and Cu/Zn, whereas age was associated with Cu, I, Mg, Mo, and Cu/Zn, whereas gender accounted only for variability in serum Mn levels. Principal component analysis (PCA) also revealed significant contributions of Mg, Zn, and Cu/Zn values to ADHD variability. CONCLUSIONS: Hypothetically, the observed decrease of essential trace elements, namely Mg and Zn, and elevation of Cu/Zn may significantly contribute to the risk of ADHD or its severity and/or comorbidity.

Analysis of Density-Functional Errors for Noncovalent Interactions between Charged Molecules.

The study of the structure and chemistry of biological systems with density-functional theory requires an accurate description of intermolecular interactions involving charged moieties. While dispersion-corrected functionals accurately model noncovalent interactions in neutral systems, a systematic study of the performance and errors associated with intermolecular interactions between charged fragments is missing. We undertake this study by examining the performance of a series of dispersion-corrected functionals with varying degrees of exact exchange for the side-chain protein interactions from the BioFragment Database (BFDb) of Burns et al. (the SSI set). In general, hybrid functionals with 20-30% exact exchange are accurate across the board, with the lowest mean absolute errors of 0.11 kcal/mol obtained from the 20% exact-exchange BLYP and PW86PBE hybrids coupled with the exchange-hole dipole moment (XDM) dispersion model. In addition, our analysis shows that functionals with higher exact-exchange fractions overestimate the electrostatic contributions to the binding energies, and that GGA functionals overestimate zwitterion binding energies due to delocalization error and overestimated charge transfer. In addition, the (quite large) repulsion in the dications is systematically overestimated by all functionals, and the trends for the monoanionic and dianionic dimers can be successfully explained by appealing to the ability of the underlying GGA to describe Pauli repulsion, as given by its exchange enhancement factor. Going beyond studies of biomolecules, this latter result has important implications for selecting appropriate GGA functionals for applications to ionic solids and layered materials containing anion-anion interactions.

Fifteen shades of green: The evolution of Bufotes toads revisited.

The radiation of Palearctic green toads (Bufotes) holds great potential to evaluate the role of hybridization in phylogeography at multiple stages along the speciation continuum. With fifteen species representing three ploidy levels, this model system is particularly attractive to examine the causes and consequences of allopolyploidization, a prevalent yet enigmatic pathway towards hybrid speciation. Despite substantial efforts, the evolutionary history of this species complex remains largely blurred by the lack of consistency among the corresponding literature. To get a fresh, comprehensive view on Bufotes phylogeography, here we combined genome-wide multilocus analyses (RAD-seq) with an extensive compilation of mitochondrial, genome size, niche modelling, distribution and phenotypic (bioacoustics, morphometrics, toxin composition) datasets, representing hundreds of populations throughout Eurasia. We provide a fully resolved nuclear phylogeny for Bufotes and highlight exceptional cyto-nuclear discordances characteristic of complete mtDNA replacement (in 20% of species), mitochondrial surfing during post-glacial expansions, and the formation of homoploid hybrid populations. Moreover, we traced the origin of several allopolyploids down to species level, showing that all were exclusively fathered by the West Himalayan B. latastii but mothered by several diploid forms inhabiting Central Asian lowlands, an asymmetry consistent with hypotheses on mate choice and Dobzhansky-Muller incompatibilities. Their intermediate call phenotypes potentially allowed for rapid reproductive isolation, while toxin compositions converged towards the ecologically-closest parent. Across the radiation, we pinpoint a stepwise progression of reproductive isolation through time, with a threshold below which hybridizability is irrespective of divergence (<6My), above which species barely admix and eventually evolve different mating calls (6-10My), or can successfully cross-breed through allopolyploidization (>15My). Finally, we clarified the taxonomy of Bufotes (including genetic analyses of type series) and formally described two new species, B. cypriensis sp. nov. (endemic to Cyprus) and B. perrini sp. nov. (endemic to Central Asia). Embracing the genomic age, our framework marks the advent of a new exciting era for evolutionary research in these iconic amphibians.

Dispersion XDM with Hybrid Functionals: Delocalization Error and Halogen Bonding in Molecular Crystals.

The accurate calculation of relative lattice energies of molecular crystals is important in polymorph ranking and crystal structure prediction. Delocalization error has been shown to affect calculated intermolecular binding energies in DFT and is similarly expected to affect the lattice energies of some classes of molecular crystals. In this work, we explore the use of dispersion-corrected hybrid functionals in the planewave-pseudopotentials approach to reduce delocalization error. We combine several hybrid functionals with the exchange-hole dipole moment (XDM) model for dispersion and show that they generally outperform GGA functionals in the calculation of both gas-phase binding energies and molecular crystal lattice energies. We apply the resulting XDM-corrected functionals to four halogen-bonded crystals: Cl2, Br2, I2, and ICl. GGA functionals severely overestimate their lattice energies, while hybrid functionals give accurate values. The preference of GGA functionals for monatomic structures in the Br2 and Cl2 crystals is also explained. Finally, we apply a recently developed method to calculate Bader's delocalization indices to examine the extent of intermolecular delocalization in the halogen molecular crystals. It is shown that intermolecular delocalization indices can be used to measure the strength of halogen bonds within the crystal, as well as detect the presence of delocalization error.

Gold(i) sulfide: unusual bonding and an unexpected computational challenge in a simple solid.

We report the experimental high-pressure crystal structure and equation of state of gold(i) sulfide (Au2S) determined using diamond-anvil cell synchrotron X-ray diffraction. Our data shows that Au2S has a simple cubic structure with six atoms in the unit cell (four Au in linear, and two S in tetrahedral, coordination), no internal degrees of freedom, and relatively low bulk modulus. Despite its structural simplicity, Au2S displays very unusual chemical bonding. The very similar and relatively high electronegativities of Au and S rule out any significant metallic or ionic character. Using a simple valence bond (Lewis) model, we argue that the Au2S crystal possesses two different types of covalent bonds: dative and shared. These bonds are distributed in such a way that each Au atom engages in one bond of each kind. The multiple arrangements in space of dative and shared bonds are degenerate, and the multiplicity of configurations imparts the system with multireference character, which is highly unusual for an extended solid. The other striking feature of this system is that common computational (DFT) methods fail quite spectacularly to describe it, with 20% and 400% errors in the equilibrium volume and bulk modulus, respectively. We explain this by the poor treatment of static correlation in common density-functional approximations. The fact that the solid is structurally very simple, yet presents unique chemical bonding and is unmodelable using current DFT methods, makes it an interesting case study and a computational challenge.

Quantitative Electron Delocalization in Solids from Maximally Localized Wannier Functions.

Electron delocalization is the quantum-mechanical principle behind chemical concepts such as aromaticity, resonance, and bonding. A common way to measure electron delocalization in the solid state is through the visualization of maximally localized Wannier functions, a method similar to using localized orbitals in molecular quantum chemistry. Although informative, this method can only provide qualitative information and is essentially limited by the arbitrariness in the choice of orbital rotation. Quantitative orbital-independent interatomic delocalization indices can be calculated by integration inside of atomic regions of probability densities obtained from the system's wave function. In particular, Bader's delocalization indices are very informative, but typically expensive to calculate. In this article, we present a fast method to obtain the localization and delocalization indices in a periodic solid under the plane-wave/pseudopotential approximation. The efficiency of the proposed method hinges on the use of grid-based atomic integration techniques and maximally localized Wannier functions. The former enables the rapid calculation of all atomic overlap integrals required in the construction of the delocalization indices. The latter allows discarding the overlaps between maximally localized Wannier functions whose centers are far enough apart. Using the new method, all localization and delocalization indices in solids with dozens of atoms can be calculated in hours on a desktop computer. Illustrative examples are presented and studied: some simple and molecular solids, polymeric nitrogen, intermolecular delocalization in 10 phases of ice, and the self-ionization of ammonia under pressure. This work is an important step toward the quantitative description of chemical bonding in solids under pressure.