Increased Evolutionary Rate in the Z chromosome of Sympatric and Allopatric Species of Morpho Butterflies.

Divergent evolution of genomes among closely related species is shaped by both neutral processes and ecological forces, such as local adaptation and reinforcement. These factors can drive accelerated evolution of sex chromosomes relative to autosomes. Comparative genomic analyses between allopatric and sympatric species with overlapping or divergent ecological niches offer insights into reinforcement and ecological specialization on genome evolution.

Exploring polymorphism in a palatable prey: predation risk and frequency dependence in relation to distinct levels of conspicuousness.

Camouflage and warning signals are different antipredator strategies, which offer an excellent opportunity to study the evolutionary forces acting on prey appearance. Edible prey often escape detection via camouflage, which usually leads to apostatic selection favoring rare morphs. By contrast, defended prey often display conspicuous coloration acting as warning signals to predators, which usually leads to positive frequency dependence and signal uniformity.

Informative Training Data for Efficient Property Prediction in Metal-Organic Frameworks by Active Learning.

In recent data-driven approaches to material discovery, scenarios where target quantities are expensive to compute and measure are often overlooked. In such cases, it becomes imperative to construct a training set that includes the most diverse, representative, and informative samples. Here, a novel regression tree-based active learning algorithm is employed for such a purpose.

Four new species of Indasclera vihla from the Oriental Region (Coleoptera: Oedemeridae).

Four new species of Indasclera vihla, 1980 are described and illustrated: Indasclera bipartita n. sp. from Laos, I.

Perspective from a Hubbard U-density corrected scheme towards a spin crossover-mediated change in gas affinity.

By employing a recently proposed Hubbard U density-corrected scheme within density functional theory, we provide design principles towards the design of materials exhibiting a spin crossover-assisted gas release. Small molecular fragments are used as case study to identify two main mechanisms behind the change in binding energy upon spin transitions. The feasibility of the proposed mechanism in porous crystals is assessed by correlating the change in binding energy of CO2, CO, N2, and H2, upon spin crossover, with the adiabatic energy difference associated with the spin state change of the square-planar metal in Hofmann-type clathrates (M = Fe, Mn, Ni).

Artificial Neural Network-Based Density Functional Approach for Adiabatic Energy Differences in Transition Metal Complexes.

During the past decades, approximate Kohn-Sham density functional theory schemes have garnered many successes in computational chemistry and physics, yet the performance in the prediction of spin state energetics is often unsatisfactory. By means of a machine learning approach, an enhanced exchange and correlation functional is developed to describe adiabatic energy differences in transition metal complexes. The functional is based on the computationally efficient revision of the regularized, strongly constrained, and appropriately normed functional and improved by an artificial neural network correction trained over a small data set of electronic densities, atomization energies, and/or spin state energetics.

CO and CO adsorption mechanism in Fe(pz)[Pt(CN)] probed by neutron scattering and density-functional theory calculations.

We study the binding mechanism of CO and CO in the porous spin-crossover compound Fe(pz)[Pt(CN)] by combining neutron diffraction (ND), inelastic neutron scattering (INS) and density-functional theory (DFT) calculations. Two adsorption sites are identified, above the open-metal site and between the pyrazine rings. For CO adsorption, the guest molecules are parallel to the neighboring gas molecules and perpendicular to the pyrazine planes.

Assessing the Role of the Kohn-Sham Density in the Calculation of the Low-Lying Bethe-Salpeter Excitation Energies.

We adopt the many-body perturbation theory in conjunction with the Bethe-Salpeter equation (BSE) to compute 57 excitation energies of a set of 37 molecules. By using the PBEh global hybrid functional and a self-consistent scheme on the eigenvalues in , we show a strong dependence of the BSE energy on the starting Kohn-Sham (KS) density functional. This arises from both the quasiparticle energies and the spatial localization of the frozen KS orbitals employed to compute the BSE.

The false-blister beetles (Coleoptera, Oedemeridae) of Oman with the description of a new species.

This paper is the first to deal with the false-blister beetle of the sultanate of Oman: it provides an overview of the biogeography of the country and an annotated checklist of the eight known species, four of which are new for Oman. In addition, a new species, Probosca (Proboxantha) coniuncta n. sp.

Tunable Proton Conductivity and Color in a Nonporous Coordination Polymer via Lattice Accommodation to Small Molecules.

Nonporous coordination polymers (npCPs) able to accommodate molecules through internal lattice reorganization are uncommon materials with applications in sensing and selective gas adsorption. Proton conduction, extensively studied in the analogue metal-organic frameworks under high-humidity conditions, is however largely unexplored in spite of the opportunities provided by the particular sensitivity of npCPs to lattice perturbations. Here, AC admittance spectroscopy is used to unveil the mechanism behind charge transport in the nonporous 1·2CH CN.

Twin boundary migration in an individual platinum nanocrystal during catalytic CO oxidation.

At the nanoscale, elastic strain and crystal defects largely influence the properties and functionalities of materials. The ability to predict the structural evolution of catalytic nanocrystals during the reaction is of primary importance for catalyst design. However, to date, imaging and characterising the structure of defects inside a nanocrystal in three-dimensions and in situ during reaction has remained a challenge.

Electric field-induced oxygen vacancies in YBaCuO.

The microscopic doping mechanism behind the superconductor-to-insulator transition of a thin film of YBaCuO was recently identified as due to the migration of O atoms from the CuO chains of the film. Here, we employ density-functional theory calculations to study the evolution of the electronic structure of a slab of YBaCuO in the presence of oxygen vacancies under the influence of an external electric field. We find that, under massive electric fields, isolated O atoms are pulled out of the surface consisting of CuO chains.

Strongly Bound Excitons in Metal-Organic Framework MOF-5: A Many-Body Perturbation Theory Study.

During the past years, one of the most iconic metal-organic frameworks (MOFs), MOF-5, has been characterized as a semiconductor by theory and experiments. Here we employ the many-body perturbation theory in conjunction with the Bethe-Salpeter equation to compute the electronic structure and optical properties of this MOF. The calculations show that MOF-5 is a wide-band-gap insulator with a fundamental gap of ∼8 eV.

Improved Spin-State Energy Differences of Fe(II) Molecular and Crystalline Complexes the Hubbard -Corrected Density.

We recently showed that the DFT+U approach with a linear-response yields adiabatic energy differences biased toward high spin [Mariano . , 6755-6762]. Such bias is removed here by employing a density-corrected DFT approach where the PBE functional is evaluated on the Hubbard -corrected density.

Biased Spin-State Energetics of Fe(II) Molecular Complexes within Density-Functional Theory and the Linear-Response Hubbard Correction.

The spin-state energetics of six Fe(II) molecular complexes are computed using the linear-response Hubbard approach within DFT. The adiabatic energy differences, Δ, between the high-spin ( = 2) and the low-spin ( = 0) states are computed and compared with accurate-coupled cluster-corrected CASPT2 results. We show that DFT+U fails in correctly capturing the ground state for strong-field ligands yielding Δ that are almost constant throughout the molecular series.

Response of native and exotic longhorn beetles to common pheromone components provides partial support for the pheromone-free space hypothesis.

Longhorn beetles are among the most important groups of invasive forest insects worldwide. In parallel, they represent one of the most well-studied insect groups in terms of chemical ecology. Longhorn beetle aggregation-sex pheromones are commonly used as trap lures for specific and generic surveillance programs at points of entry and may play a key role in determining the success or failure of exotic species establishment.

Divergent Adsorption-Dependent Luminescence of Amino-Functionalized Lanthanide Metal-Organic Frameworks for Highly Sensitive NO Sensors.

A novel gas sensing mechanism exploiting lanthanide luminescence modulation upon NO adsorption is demonstrated here. Two isostructural lanthanide-based metal-organic frameworks (MOFs) are used, including an amino group as the sensitive recognition center for NO molecules. The transfer of energy from the organic ligands to Ln is strongly dependent on the presence of NO, resulting in an unprecedented photoluminescent sensing scheme.

Accurate Prediction of the S Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations.

By employing the Bethe-Salpeter formalism coupled with a nonequilibrium embedding scheme, we demonstrate that the paradigmatic case of S band separation between and in azobenzene derivatives can be computed with excellent accuracy compared to experimental optical spectra. Besides embedding, we show that the choice of the Kohn-Sham exchange correlation functional for DFT is critical, despite the iterative convergence of quasiparticle energies. We address this by adopting an orbital-tuning approach via the global hybrid functional, PBEh, yielding an environment-consistent ionization potential.

A new Ischnomera of the I. xanthoderes (Mulsant, 1858) complex (Coleoptera: Oedemeridae) from Sicily.

A new Ischnomera from northern Sicily is described. Besides this species, in the western Mediterranean I. xanthoderes complex were distinct one species from the Iberian peninsula and southern France (I.

A switchable iron-based coordination polymer toward reversible acetonitrile electro-optical readout.

Efficient and low cost detection of harmful volatile organic compounds (VOCs) is a major health and environmental need in industrialized societies. For this, tailor-made porous coordination polymers are emerging as promising molecular sensing materials thanks to their responsivity to a wide variety of external stimuli and could be used to complement conventional sensors. Here, a non-porous crystalline 1D Fe(ii) coordination polymer acting as a porous acetonitrile host is presented.

Probing the electric field-induced doping mechanism in YBaCuO using computed Cu K-edge x-ray absorption spectra.

We recently demonstrated that the superconductor-to-insulator transition induced by ionic liquid gating of the high temperature superconductor YBaCuO (YBCO) is accompanied by a deoxygenation of the sample [A. M. Perez-Munoz , Proc.

Tuning Gas Adsorption by Metal Node Blocking in Photoresponsive Metal-Organic Frameworks.

By combining first-principles calculations and classical molecular simulations, an atomistic-level of understanding was provided towards the notable change in CO adsorption upon light treatment in two recently reported photoactive metal-organic frameworks, PCN-123 and Cu (AzoBPDC) (AzoBiPyB). It was demonstrated that the reversible decrease in gas adsorption upon isomerization can be primarily attributed to the blocking of the strong adsorbing sites at the metal nodes by azobenzene molecules in a cis configuration. The same mechanism was found to apply also to other molecules, for example, alkanes and toxic gases.

In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X.

Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer.

Probing gas adsorption in MOFs using an efficient ab initio widom insertion Monte Carlo method.

We propose a novel biased Widom insertion method that can efficiently compute the Henry coefficient, K , of gas molecules inside porous materials exhibiting strong adsorption sites by employing purely DFT calculations. This is achieved by partitioning the simulation volume into strongly and weakly adsorbing regions and selectively biasing the Widom insertion moves into the former region. We show that only few thousands of single point energy calculations are necessary to achieve accurate statistics compared to many hundreds of thousands or millions of such calculations in conventional random insertions.