Triaryl-1,3,5-triazinane-2,4,6-triones functionalized with electron-rich Fe(II) and Ru(II) acetylide complexes: new organometallic octupoles with large hyperpolarizabilities

The synthesis and study of a series of trinuclear organometallic triaryl-1,3,5-triazinane-2,4,6-triones functionalized by d(6)-transition metal acetylides complexes at their periphery are reported. Remarkably large hyperpolarizabilities, far superior to those of related purely organic derivatives, are measured by hyper-Rayleigh scattering (HRS) for these new octupolar chromophores.     

An adaptive SPH method for strong shocks

We propose an alternative SPH scheme to usual SPH Godunov-type methods for simulating supersonic compressible flows with sharp discontinuities. The method relies on an adaptive density kernel estimation (ADKE) algorithm, which allows the width of the kernel interpolant to vary locally in space and time so that the minimum necessary smoothing is applied in regions of low density. We have performed a von Neumann stability analysis of the SPH equations for an ideal gas and derived the corresponding dispersion relation in terms of the local width of the kernel. Solution of the dispersion relation in the short wavelength limit shows that stability is achieved for a wide range of the ADKE parameters. Application of the method to high Mach number shocks confirms the predictions of the linear analysis. Examples of the resolving power of the method are given for a set of difficult problems, involving the collision of two strong shocks, the strong shock-tube test, and the interaction of two blast waves.     

Unprecedented Solvent‐Assisted Reactivity of Hydrido W3CuS4 Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit

Opening the cluster core : Substitution of the chloride ligand in the novel cationic cluster [W₃CuS₄H₃Cl(dmpe)₃]⁺ (see figure; dmpe=1,2‐bis(dimethylphosphino)ethane) by acetonitrile is promoted by water addition. Kinetic and density functional theory studies lead to a mechanistic proposal in which acetonitrile or water attack causes the opening of the cluster core with dissociation of one of the Cu? S bonds to accommodate the entering ligand.

     

Modeling the heating of biological tissue based on the hyperbolic heat transfer equation

In modern surgery, a multitude of minimally intrusive operational techniques are used which are based on the point heating of target zones of human tissue via laser or radiofrequency currents. Traditionally, these processes are modeled by the bioheat equation introduced by Pennes, who considers Fourier’s theory of heat conduction. We present an alternative and more realistic model established using the hyperbolic equation of heat transfer. To demonstrate some features and advantages of our proposed method, we apply the results obtained to different types of tissue heating with high energy fluxes, in particular radiofrequency heating and pulsed laser treatment of the cornea to correct refractive errors. We hope that the results from our approach will help with refining surgical interventions in this novel field of medical treatment.     

Understanding Regium Bonds and their Competition with Hydrogen Bonds in Au2:HX Complexes

A theoretical study of the regium and hydrogen bonds (RB and HB, respectively) in Au₂:HX complexes has been carried out by means of CCSD(T) calculations. The theoretical study shows as overall outcome that in all cases the complexes exhibiting RB are more stable that those with HB. The binding energies for RB complexes range between −24 and −180 kJ ⋅ mol^−1, whereas those of the HB complexes are between −6 and −19 kJ ⋅ mol⁻¹. DFT-SAPT also indicated that HB complexes are governed by electrostatics, but RB complexes present larger contribution of the induction term to the total attractive forces. ¹⁹⁷Au chemical shifts have been calculated using the relativistic ZORA Hamiltonian.     

Thermalization of Isolated Bose‐Einstein Condensates by Dynamical Heat Bath Generation

If and how an isolated quantum system thermalizes despite its unitary time evolution is a long‐standing, open problem of many‐body physics. The eigenstate thermalization hypothesis (ETH) postulates that thermalization happens at the level of individual eigenstates of a system's Hamiltonian. However, the ETH requires stringent conditions to be validated, and it does not address how the thermal state is reached dynamically from an initial non‐equilibrium state. We consider a Bose‐Einstein condensate (BEC) trapped in a double‐well potential with an initial population imbalance. We find that the system thermalizes although the initial conditions violate the ETH requirements. We identify three dynamical regimes. After an initial regime of undamped Josephson oscillations, the subsystem of incoherent excitations or quasiparticles (QP) becomes strongly coupled to the BEC subsystem by means of a dynamically generated, parametric resonance. When the energy stored in the QP system reaches its maximum, the number of QPs becomes effectively constant, and the system enters a quasi‐hydrodynamic regime where the two subsystems are weakly coupled. In this final regime the BEC acts as a grand‐canonical heat reservoir for the QP system (and vice versa), resulting in thermalization. We term this mechanism dynamical bath generation (DBG).     

The influence of short‐chain branching on the morphology and structure of polyethylene single crystals

The influence of short‐chain branching on the formation of single crystals at constant supercooling is systematically studied in a series of metallocene catalyzed high‐molecular‐weight polyethylene samples. A strong effect of short‐chain branching on the morphology and structure of single crystals is reported. An increase of the axial ratio with short‐chain branching content, together with a characteristic curvature of the (110) crystal faces are observed. To the best of our knowledge, this is the first time that this observation is reported in high‐molecular‐weight polyethylene. The curvature can be explained by a continuous increase in the step initiation—step propagation rates ratio with short‐chain branching, that is, nucleation events are favored against stem propagation by the presence of chain defects. Micro‐diffraction and WAXS results clearly indicate that all samples crystallize in the orthorhombic form. An increase of the unit cell parameter a₀ is detected, an effect that is more pronounced than in the case of single crystals with ethyl and propyl branches. The changes observed are compatible with an expanded lattice due to the presence of branches at the surface folding. A decrease in crystal thickness with branching content is observed as determined from shadow measurements by TEM. The results are in agreement with additional SAXS results performed in single crystal mats and with indirect calorimetry measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1751–1762