Shock structure in the 14 moment system of extended thermodynamics with high order closure based on the maximum entropy principle

Ricerche di Matematica - An analysis of the shock structure in the 14 moment system of extended thermodynamics with first, second and third order closure based on the maximum entropy principle...     

Local Approximation from Spline Spaces on Box Meshes

Foundations of Computational Mathematics - This paper analyzes the approximation properties of spaces of piecewise tensor product polynomials over box meshes with a focus on application to...     

Periodic Golay pairs and pairwise balanced designs

Journal of Algebraic Combinatorics - In this paper we exploit a relationship between certain pairwise balanced designs with v points and periodic Golay pairs of length v, to classify periodic Golay...     

A Chemically Soldered Polyoxometalate Single-Molecule Transistor

Polyoxometalates have been proposed in the literature as nanoelectronic components, where they could offer key advantages with their structural versatility and rich electrochemistry. Apart from a few studies on their ensemble behaviour (as monolayers or thin films), this potential remains largely unexplored. We synthesised a pyridyl-capped Anderson–Evans polyoxometalate and used it to fabricate single-molecule junctions, using the organic termini to chemically “solder” a single cluster to two nanoelectrodes. Operating the device in an electrochemical environment allowed us to probe charge transport through different oxidation states of the polyoxometalate, and we report here an efficient three-state transistor behaviour. Conductance data fits a quantum tunnelling mechanism with different charge-transport probabilities through different charge states. Our results show the promise of polyoxometalates in nanoelectronics and give an insight on their single-entity electrochemical behaviour.     

Sextic centrifugal distortion constants: interplay of density functional and basis set for accurate yet feasible computations

Quantum-chemical calculations assist the analysis of laboratory spectra, and often provide the only means to determine spectroscopic data that cannot be accessed experimentally. Accurate predictions of vibrational and rotational spectroscopic parameters are required for applications in the field of high-resolution molecular spectroscopy. While the accuracy issue of the quantum-chemical calculation of vibrational properties and of equilibrium structures has been addressed in the literature, the same is not true for centrifugal distortion constants that however play an essential role for the interpretation of remote sensing data. In this work, the performance of several model chemistries, rooted mainly in density functional theory, in computing sextic centrifugal distortion constants is assessed employing a benchmark set of molecules of both atmospheric and astrochemical relevance. The Jensen’s (aug-)pcs-n basis sets, different flavours of Dunning’s triple-ζ basis sets and the SNSD basis set, are employed in conjunction with different functionals, and their predictions are benchmarked against experimental and theoretical data at the coupled cluster level of theory. This study also demonstrates the reliability of the calculation of sextic centrifugal distortion constants within the Gaussian16 rev. B.01 program package. Reliable predictions of the sextic centrifugal distortion constants for the gauche- and trans-conformers of ethyl-mercaptan are also presented.     

Fracture behavior and mechanical,thermal, and rheological properties of biodegradable films extruded by flat die and calender

The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.     

Study of spatial inhomogeneity in inverted all‐polymer solar cells: Effect of solvent and annealing

The efficiency optimization of bulk heterojunction solar cells requires the control of the local active materials arrangement in order to obtain the best compromise between efficient charge generation and charge collection. Here, we investigate the large scale (10–100 μm) inhomogeneity of the photoluminescence (PL) and the external quantum efficiency (EQE) in inverted all‐polymer solar cells (APSC) with regioregular poly(3‐hexylthiophene) (P3HT):poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) active blends. The morphology and the local active polymer mixing are changed by depositing the active layer from four different solvents and by thermal annealing. The simultaneous PL and EQE mapping allowed us to inspect the effects of local irregularities of active layer thickness, polymer mixing, polymer aggregation on the charge generation and collection efficiencies. In particular, we show that the increase of the solvent boiling point affects the EQE non‐uniformity due to thickness fluctuations, the density non‐uniformity of rrP3HT aggregate phase, and the blend components clustering. The thermal annealing leads to a general improvement of EQE and to an F8BT clustering in all the samples with locally decrease of the EQE. We estimate that the film uniformity optimization can lead to a total EQE improvement between 2.7 and 6.3 times. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 804–813     

The Landscape of the Spiked Tensor Model

We consider the problem of estimating a large rank-one tensor u ^⊗k ∈ (ℝⁿ)^⊗k , k ≥ 3 , in Gaussian noise. Earlier work characterized a critical signal-to-noise ratio λ  _Bayes = O(1) above which an ideal estimator achieves strictly positive correlation with the unknown vector of interest. Remarkably, no polynomial-time algorithm is known that achieved this goal unless λ ≥ Cn^{(k − 2)/4} , and even powerful semidefinite programming relaxations appear to fail for 1 ≪ λ ≪ n^{(k − 2)/4} . In order to elucidate this behavior, we consider the maximum likelihood estimator, which requires maximizing a degree-k homogeneous polynomial over the unit sphere in n dimensions. We compute the expected number of critical points and local maxima of this objective function and show that it is exponential in the dimensions n , and give exact formulas for the exponential growth rate. We show that (for λ larger than a constant) critical points are either very close to the unknown vector u or are confined in a band of width Θ(λ^{−1/(k − 1)}) around the maximum circle that is orthogonal to u . For local maxima, this band shrinks to be of size Θ(λ^{−1/(k − 2)}) . These “uninformative” local maxima are likely to cause the failure of optimization algorithms. © 2019 Wiley Periodicals, Inc.