Binding of hydrogen on benzene, coronene, and graphene from quantum Monte Carlo calculations

Quantum Monte Carlo calculations with the diffusion Monte Carlo (DMC) method have been used to compute the binding energy curves of hydrogen on benzene, coronene, and graphene. The DMC results on benzene agree with both M?ller-Plessett second order perturbation theory (MP2) and coupled cluster with singles, doubles, and perturbative triples [CCSD(T)] calculations, giving an adsorption energy of ～25 meV. For coronene, DMC agrees well with MP2, giving an adsorption energy of ～40 meV. For physisorbed hydrogen on graphene, DMC predicts a very small adsorption energy of only 5 ± 5 meV. Density functional theory (DFT) calculations with various exchange-correlation functionals, including van der Waals corrected functionals, predict a wide range of binding energies on all three systems. The present DMC results are a step toward filling the gap in accurate benchmark data on weakly bound systems. These results can help us to understand the performance of current DFT based methods, and may aid in the development of improved approaches.     

Exploring the accuracy level of new potential energy surfaces for the F + HD reactions: from exact quantum rate constants to the state-to-state reaction dynamics

Exact quantum reactive scattering calculations in the collision energy range 1-250 meV have been carried out for both the isotopic product channels of the title system. The dynamical studies compares an ab initio potential energy surface (PES) recently appeared in the literature (J. Chem. Phys., 2008, 129, 011103) with other phenomenological PESs. Vibrational branching ratios, cross sections and rate constants are presented and compared with molecular beam scattering experiments as well as with chemical kinetics data. In particular, the agreement of the vibrational branching ratios with experimental measurements is improved with respect to previous studies on other PESs, mainly because of the presence of a broad peak in the HF(v' = 3) integral cross section completely absent in the previous simulations. This feature, observed by molecular beam experiments, is the fingerprint of a new reaction mechanism operative in the dynamics described by the new PES. A conjecture for its origin, able to explain many of its characteristic aspects, is analyzed and discussed.     

Efficient crystallization induced emissive materials based on a simple push-pull molecular structure

Solid state luminescent materials are the subject of ever growing interest both from a scientific and a technological point of view. Aggregation caused quenching (ACQ) processes however represent an obstacle to the development of most luminogens in the condensed phase. This is why particularly fascinating are those materials showing higher emission intensity in the solid state than in solution. Here we report on three 4-dialkylamino-2-benzylidene malonic acid dialkyl esters, very simple push-pull molecules, which are hardly emissive in solution and in the amorphous phase but become good emitters in the crystalline phase according to what has been indicated as crystallization induced emission (CIE). Thanks to combined emission and NMR spectroscopies at different temperatures on the prototype compound 4-dimethylamino-2-benzylidene malonic acid dimethyl ester in solution, we give full evidence that a restricted intramolecular rotation (RIR) phenomenon, in particular the hindered rotation around the aryl main axis of the compound, is at the origin of this behaviour. In addition, solid state photophysical and X-ray diffraction structural characterization allow us to identify J-dimeric interactions as responsible for the particularly intense emission of two of the three compounds. Moreover, by exploiting the compounds' acidochromic properties, applications in sensors and optoelectronics are envisaged.     

Anthraquinone profile, antioxidant and antimicrobial properties of bark extracts of Rhamnus catharticus and R. orbiculatus

The anthraquinone profile, antioxidant and antimicrobial activities as well as the total phenol and total flavonoid contents were determined in methanol extracts of the barks of Rhamnus catharticus L. and R. orbiculatus Bornm. The most abundant anthraquinone derivatives in R. catharticus were physcion (67.8%) and emodin (26.2%), while R. orbiculatus contained mostly physcion (81.3%) and chrysophanol (14.6%). R. catharticus displayed better activity in the beta-carotene-linoleic acid assay, as well as chelating activity, whereas its activity in the reducing power assay was significantly lower than that of R. orbiculatus. Both methanol extracts showed antimicrobial activity against all microbial species tested (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Candida albicans, Aspergillus niger, Microsporum gypseum) with MIC values either equal to or lower than 2.50 mg/mL. R. catharticus and R. orbiculatus contained several anthranoid aglycones and their bark extracts demonstrated notable antioxidant and antimicrobial properties. The results obtained indicate the medicinal potential of these two species.     

A generalized integro-differential theory of nonlocal elasticity of n-Helmholtz type—part II: boundary-value problems in the one-dimensional case

Meccanica - This paper is the second in a series of two that deal with a generalized theory of nonlocal elasticity of n-Helmholtz type. This terminology is motivated by the fact that the...     

A new belt-type apparatus for neutron-based rheological measurements at gigapascal pressures

We have developed a new solid-media apparatus for performing rheological investigations at multi-gigapascal pressures. The pressure cell consists of a simple belt design and fits in a modified 250 tonne Paris–Edinburgh press. Elastic strains are measured by neutron diffraction, on the ENGIN-X experimental station at ISIS. Stresses are estimated from the measured strains in combination with published values of the elastic moduli. As an exemplair of the method, we present data from initial deformation experiments on pyrope garnet at 1.5 GPa and 873 K. Data collection times are as short as 60 min and the elastic strain resolution is better than 10^?4. We anticipate, however, that by interrupted testing, strain rates as low as 10^?9/s, or lower, will be measurable.     

Existence of proper semihypergroups of type U on the right

We generalize the classical definition of hypergroups of type U on the right to semihypergroups, and we prove some properties of their subsemihypergroups and subhypergroups. In particular, we obtain that a finite proper semihypergroup of type U on the right can exist only if its order is at least 6. We prove that one such semihypergroup of order 6 actually exists. Moreover, we show that there exists a hypergroup of type U on the right of cardinality 9 containing a proper non-trivial subsemihypergroup. In this way, we solve a problem left open in [D. Freni, Sur les hypergroupes de type U et sous-hypergroupes engendrés par un sous-ensemble, Riv. Mat. Univ. Parma 13 (1987) 29-41].     

On Metastability in FPU

We present an analytical study of the Fermi–Pasta–Ulam (FPU) α–model with periodic boundary conditions. We analyze the dynamics corresponding to initial data with one low frequency Fourier mode excited. We show that, correspondingly, a pair of KdV equations constitute the resonant normal form of the system. We also use such a normal form in order to prove the existence of a metastability phenomenon. More precisely, we show that the time average of the modal energy spectrum rapidly attains a well defined distribution corresponding to a packet of low frequencies modes. Subsequently, the distribution remains unchanged up to the time scales of validity of our approximation. The phenomenon is controlled by the specific energy.     

Effects of disorder on propagation losses and cavity Q-factors in photonic crystal slabs

A theoretical model of disorder for the etched holes or pillars in a generic two-dimensional photonic crystal slab is presented. This model is employed to calculate the effects of size disorder on propagation losses in linear photonic crystal waveguides as well as on quality (Q)-factors in photonic crystal nano-cavities. The main results obtained by the present theory and shown in this work are: (a) large single-mode bandwidth and low-loss (<0.1 dB/mm) propagation of light is predicted for increased-width membrane-type photonic crystal waveguides, (b) pillar-based lattices show reduced sensitivity to size fluctuations than hole-based ones, (c) the effects of disorder on cavity Q-factors are quantitatively evaluated. An extension of the model is also introduced in order to take into account the side-wall micro-roughness of the perfectly vertical holes, and preliminary results of this more general approach are discussed.