Theoretical investigation of the He-I2(E3Πg) ion-pair state: ab initio intermolecular potential and vibrational levels

We present a theoretical study on the potential energy surface and vibrational bound states of the E electronic excited state of the HeI(2) van der Waals system. The interaction energies are computed using accurate ab initio methods and large basis sets. Relativistic small-core effective core potentials in conjunction with a quintuple-zeta quality basis set are employed for the heavy iodine atoms in multireference configuration interaction calculations for the (3)A' and (3)A" states. For the representation of the potential energy surface we used a general interpolation technique for constructing potential surfaces from ab initio data based on the reproducing kernel Hilbert space method. The surface presents global and local minima for T-shaped configurations with well-depths of 33.2 and 4.6 cm(-1), respectively. Vibrational energies and states are computed through variational quantum mechanical calculations. We found that the binding energy of the HeI(2)(E) T-shaped isomer is 16.85 cm(-1), in excellent agreement with recent experimental measurements. In lieu of more experimental data we also report our predictions on higher vibrational levels and we analyze the influence of the underlying surface on them. This is the first attempt to represent the potential surface of such a highly excited electronic state of a van der Waals complex, and it demonstrates the capability of the ab initio technology to provide accurate results for carrying out reliable studies to model experimental data.     

Hydration studies in polymer hydrogels

Polymer hydrogels have attracted much interest in recent years based on numerous applications mainly in biotechnology and medicine. For the knowledge‐based design and development of new materials for these and similar applications, it is essential to understand better the hydration properties of hydrogels and of polymers in general. With this term, we mean the particular organization of water in the hydrogel, which determines the properties of the water component, typically different than those of bulk water, and the impact of water on the properties of the polymer matrix itself. In this review, we focus on recent work with hydrogels based on poly(hydroxyethyl acrylate), mostly copolymers with a second hydrophobic polymer and silica nanocomposites. The combination of water sorption/diffusion, thermal and dielectric studies, by fully exploiting the capabilities of each individual technique, proves essential in providing significant information on particular aspects of hydration, such as water uptake, water organization, and diffusion coefficients; glass transition and plasticization; water and polymer dynamics; protonic conductivity, and in revealing interesting correlations between these particular aspects. In the outlook similarities and differences to other related systems, such as protein‐water and polymer solutions in non‐polar solvents, are stressed in the perspective of a broader study. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Ab initio study of the electronic structure and bonding of aluminum nitride

For the diatomic aluminum nitride (AlN), we have constructed potential energy curves for 45 states employing multi-reference variational methods and quantitative basis sets. Thirty-six states are relatively strongly bound, five present local minima, and four are of repulsive nature. Almost all states are of intense multi-reference character rendering their calculation and interpretation quite problematic. Our tentative assignment of the ground state is 3Pi, while a 3Sigma- state is above by less than 1 kcal/mol. Our best estimate for the binding energy of the X3Pi state is D0 = 56.0 +/- 0.5 kcal/mol at re = 1.783 A, in good agreement with the experimental values of D = 66 +/- 9 kcal/mol and re = 1.7864 A. The binding energy of the A3Sigma- state is very similar to the X state because they both correlate to the ground-state atoms, but the bond distance of the former is 0.13 A longer. The first seven states can be tagged as follows: X3Pi, A3Sigma-, a1Sigma+, b1Pi, c1Delta, B3Sigma+, and d1Sigma+, a rather definitive order with the exception of X and A states.     

Molecular dynamics in nanostructured polyimide-silica hybrid materials and their thermal stability

Molecular motion and thermal stability in two series of nanophase-separated polyimide-silica (PI-SiO₂) hybrid networks with chemically bound components were studied. The hybrids were prepared via a sol-gel process and differed in PI structure and chain length, and in SiO₂ content ranging from 10 to 50 wt.%. Differential scanning calorimetry, laser-interferometric creep rate spectroscopy, dielectric relaxation spectroscopy, thermally stimulated depolarization current techniques, and thermogravimetry were used covering, on the whole, the ranges of 100–900 K and 10⁻³-10⁹ Hz. Silica domains influenced PI dynamics in two opposite directions. Loosened segmental packing in chains confined to nanovolumes resulted mainly in rise of small-scale motion below β-relaxation region, while anchoring of chain ends to ‘rigid walls’ caused, contrarily, a partial or total suppression of segmental motion above T_β, especially drastically at the temperatures close to and within glass transition. The latter resulted in a large change in thermal stability, e.g., 2.5-fold increasing of the apparent activation energy of thermooxidative degradation, and more than 100° rise of predicted long-term thermal stability for the hybrids as compared to that for PI.     

Synthesis,characterization and self‐assembly of well‐defined linear heptablock quaterpolymers

Two well‐defined heptablock quaterpolymers of the ABCDCBA type [Α: polystyrene (PS), B: poly(butadiene) with ～90% 1,4‐microstructure (PB_1,4), C: poly(isoprene) with ～55% 3,4‐microstructure (PI_3,4) and D: poly(dimethylsiloxane) (PDMS)] were synthesized by combining anionic polymerization high vacuum techniques and hydrosilylation/chlorosilane chemistry. All intermediates and final products were characterized by size exclusion chromatography, membrane osmometry, and proton nuclear magnetic resonance spectroscopy. Fourier transform infrared spectroscopy was used to further verify the chemical modification reaction of the difunctional PDMS. The self‐assembly in bulk of these novel heptablock quarterpolymers, studied by transmission electron microscopy and small angle X‐ray scattering, revealed 3‐phase 4‐layer alternating lamellae morphology of PS, PB_1,4, and mixed PI_3,4/PDMS domains. Differential scanning calorimetry was used to further confirm the miscibility of PI_3,4 and PDMS blocks. It is the first time that PDMS is the central segment in such multiblock polymers (≥3 chemically different blocks). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1443–1449     

Nonlinear optimisation using directional step lengths based on RPROP

A search method based on the backpropagation rule commonly used for training neural networks is proposed here for the optimisation of smooth nonlinear functions. The use of the Resilient backPROPagation (RPROP) heuristic rule for local minimisation is described. The details of employing the directional step length determined by RPROP along with a simple restarting scheme are provided. In the approach proposed here direct use of the directional step determined by the heuristic without using any line search conditions takes place. The overall algorithm has been tested on a number of benchmark functions found in the literature with very positive results. The test problems’ dimension ranges from 100 to 50,000. The results obtained show that the suggested search direction method results to a highly efficient algorithm suitable for large scale optimisation.     

Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB_1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory–Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations.     

Dominant three-body decays of a heavy higgs and top quark

We calculate the dominant three body Higgs decays,HW ⁺ W ^–(Z ⁰, ) and , in the Standard Model. We find that the branching ratios of these decays are of the order of few percent for large Higgs masses. We comment on the behaviour of the partial decay width below the threshold. Numerical results of the following three body top decays,tW ⁺ b(,g, Z ⁰) andtW ⁺ bH, are also given. We discuss the feasibility of observing these Higgs and top decays at future high energy colliders.