The Diamine Cation Is Not a Chemical Example Where Density Functional Theory Fails

In a recent communication, Weber and co-workers presented a surprising study on charge-localization effects in the N,N'-dimethylpiperazine (DMP+) diamine cation to provide a stringent test of density functional theory (DFT) methods. Within their study, the authors examined various DFT methods and concluded that "all DFT functionals commonly used today, including hybrid functionals with exact exchange, fail to predict a stable charge-localized state." This surprising conclusion is based on the authors' use of a self-interaction correction (namely, complex-valued Perdew-Zunger Self-Interaction Correction (PZ-SIC)) to DFT, which appears to give excellent agreement with experiment and other wavefunction-based benchmarks. Since the publication of this recent communication, the same DMP+ molecule has been cited in numerous subsequent studies as a prototypical example of the importance of self-interaction corrections for accurately calculating other chemical systems. In this correspondence, we have carried out new high-level CCSD(T) analyses on the DMP+ cation to show that DFT actually performs quite well for this system (in contrast to their conclusion that all DFT functionals fail), whereas the PZ-SIC approach used by Weber et al. is the outlier that is inconsistent with the high-level CCSD(T) (coupled-cluster with single and double excitations and perturbative triples) calculations. Our new findings and analysis for this system are briefly discussed in this correspondence.Comment: Accepted by Nature Communication

Classical properties of algebras using a new graph association

We study the relation between algebraic structures and Graph Theory. We have defined five different weighted digraphs associated to a finite dimensional algebra over a field in order to tackle important properties of the associated algebras, mainly the nilpotency and solvability in the case of Leibniz algebras

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Kovacs Effect in a Fragile Glass Model

The Kovacs protocol, based on the temperature shift experiment originally conceived by A.J. Kovacs for glassy polymers, is implemented in an exactly solvable dynamical model. This model is characterized by interacting fast and slow modes represented respectively by spherical spins and harmonic oscillator variables. Due to this fundamental property, the model reproduces the characteristic non-monotonic evolution known as the ``Kovacs effect'', observed in polymers, in granular materials and models of molecular liquids, when similar experimental protocols are implemented.Comment: 8 pages, 6 figure

Introduction: emotions and mobilities: gendered, temporal and spatial representations

Emotions are increasingly recognised as a fundamental dimension of human mobility. Indeed, there has been sustained and increasing scholarly interest in the intersection between migration and emotion over the last two decades.Theoretical and empirical contributions in this area have advanced our understanding of migration experiences in their diversity. Furthermore, viewing migrants’ lived experiences through an emotions lens can reveal a variety of hidden inequalities, unsettle hegemonic discourses and reveal practices of resistance.Perceptions of social categories such as ethnicity, gender, sexuality and age are shaped by emotions and it is therefore valuable to ‘investigate how certain emotions “stick” to certain bodies or flow and traverse space’

Management of the Rice Tungro Virus Vector \u3ci\u3eNephotettix virescens\u3c/i\u3e (Homoptera: Cicadellidae) with Controlled-Release Formulations of Carbofuran

Field trials were conducted in lowland flooded rice in the Philippines to evaluate a number of carbofuran controlled-release formulations in comparison with commercial formulations. The test formulations were based on a biodegradable matrix of pine kraft lignin and were used as granules of different sizes and also in the form of small strips. The release rates were assessed under field conditions by bioassaying rice plants in the field, using adult rice green leafhopper, Nephotettix virescens Distant. The lignin formulations with a high level of active ingredient (15–45% by weight) gave as good or better control than the commercial 3% granules in tests based on three application techniques: broadcast into the floodwater, soil incorporation, and root zone injection. The improvements in control levels of green leafhoppers were most marked with soil incorporation and root zone application. The best lignin-based formulation reduced levels of tungro virus infection from 23% for a conventional flowable carbofuran formulation to 1.0% at an application rate of 0.5 kg (AI)/ha. At the same rate, the grain yield was increased from 3.56 t/ha to 5.5 t/ha, using the controlled-released formulation

Optimal receptor-cluster size determined by intrinsic and extrinsic noise

Biological cells sense external chemical stimuli in their environment using cell-surface receptors. To increase the sensitivity of sensing, receptors often cluster, most noticeably in bacterial chemotaxis, a paradigm for signaling and sensing in general. While amplification of weak stimuli is useful in absence of noise, its usefulness is less clear in presence of extrinsic input noise and intrinsic signaling noise. Here, exemplified on bacterial chemotaxis, we combine the allosteric Monod-Wyman- Changeux model for signal amplification by receptor complexes with calculations of noise to study their interconnectedness. Importantly, we calculate the signal-to-noise ratio, describing the balance of beneficial and detrimental effects of clustering for the cell. Interestingly, we find that there is no advantage for the cell to build receptor complexes for noisy input stimuli in absence of intrinsic signaling noise. However, with intrinsic noise, an optimal complex size arises in line with estimates of the sizes of chemoreceptor complexes in bacteria and protein aggregates in lipid rafts of eukaryotic cells.Comment: 15 pages, 12 figures,accepted for publication on Physical Review

Ground state study of simple atoms within a nano-scale box

Ground state energies for confined hydrogen (H) and helium (He) atoms, inside a penetrable/impenetrable compartment have been calculated using Diffusion Monte Carlo (DMC) method. Specifically, we have investigated spherical and ellipsoidal encompassing compartments of a few nanometer size. The potential is held fixed at a constant value on the surface of the compartment and beyond. The dependence of ground state energy on the geometrical characteristics of the compartment as well as the potential value on its surface has been thoroughly explored. In addition, we have investigated the cases where the nucleus location is off the geometrical centre of the compartment.Comment: 9 pages, 5 eps figures, Revte