Homolytic vs heterolytic paths in the photochemistry of haloanilines

The photochemistry of 4-haloanilines and 4-halo-N,N-dimethylanilines has been studied in apolar, polar aprotic, and protic solvents. Photophysical and flash photolysis experiments show that the reaction proceeds in any case from the triplet state. It is rather unreactive in apolar media, the highest value being Phi = 0.05 for the iodoanilines in cyclohexane. Changing the solvent has little effect for iodoanilines and for the poorly reacting bromo analogue, while it leads to a variation of over 2 orders of magnitude in the quantum yield for the chloro and fluoro derivatives. The triplets have been characterized at the UB3LYP/6-31G(d) level of theory, evidencing a deformation and an elongation (except for C-F) of the C-X bond. Homolytic fragmentation is in every case endothermic, but calculations in acetonitrile solution show that heterolytic cleavage of C-Cl and C-Br is exothermic. Experimentally, the occurrence of heterolytic fragmentation has been monitored through selective trapping of the resulting phenyl cation by allyltrimethylsilane. Heterolytic dechlorination occurs efficiently in polar media (e.g., Phi = 0.77 in MeCN), while debromination remains ineffective due to the short lifetime of the triplet. Heterolytic defluorination is efficient only in protic solvents (Phi = 0.48 in MeOH), in accord with calculations showing that in the presence of an ancillary molecule of water fragmentation is exothermic due to the formation of the strong H-F bond. The energy profile for both homo- and heterolytic dissociation paths has been mapped along the reaction coordinates in the gas phase and in acetonitrile. The conditions determining the efficiency and mode of dehalogenation have been defined. This is significant for devising synthetic methods via photogenerated phenyl cations and for rationalizing the photodegradation of halogenated aromatic pollutants and the phototoxic effect of some fluorinated drugs.     

The Dirac-Ramond operator on loops in flat space

In this paper, a rigorous construction of the S¹-equivariant Dirac operator (i.e., Dirac-Ramond operator) on the space of (mean zero) loops in is given and its equivariant L²-index computed. Essential use is made of infinite tensor product representations of the canonical anticommutation relations algebra.     

On Norden Metrics which Are Locally Conformal to Anti-Kählerian Metrics

We build examples of Norden metrics on × S ¹, where R ^{2 n} _n is either a pseudosphere or a pseudohyperbolic space. These turn out to be locally conformal to flat anti-Kählerian metrics, strongly non anti-Kählerian, and with a parallel Lee form. Conversely, any connected complete anti-Hermitian manifold possessing these properties is shown to be locally analytically homothetic to × S ¹.     

Phase Transitions and Spatio-Temporal Fluctuations in Stochastic Lattice Lotka–Volterra Models

We study the general properties of stochastic two-species models for predator-prey competition and coexistence with Lotka–Volterra type interactions defined on a d-dimensional lattice. Introducing spatial degrees of freedom and allowing for stochastic fluctuations generically invalidates the classical, deterministic mean-field picture. Already within mean-field theory, however, spatial constraints, modeling locally limited resources, lead to the emergence of a continuous active-to-absorbing state phase transition. Field-theoretic arguments, supported by Monte Carlo simulation results, indicate that this transition, which represents an extinction threshold for the predator population, is governed by the directed percolation universality class. In the active state, where predators and prey coexist, the classical center singularities with associated population cycles are replaced by either nodes or foci. In the vicinity of the stable nodes, the system is characterized by essentially stationary localized clusters of predators in a sea of prey. Near the stable foci, however, the stochastic lattice Lotka–Volterra system displays complex, correlated spatio-temporal patterns of competing activity fronts. Correspondingly, the population densities in our numerical simulations turn out to oscillate irregularly in time, with amplitudes that tend to zero in the thermodynamic limit. Yet in finite systems these oscillatory fluctuations are quite persistent, and their features are determined by the intrinsic interaction rates rather than the initial conditions. We emphasize the robustness of this scenario with respect to various model perturbations.     

Nonlinear mobility of a driven system: Temperature and disorder effects

We consider the dissipative nonlinear dynamics of a model of interacting atoms driven over a substrate potential. The substrate parameters can be suitably tuned in order to introduce disorder effects starting from two geometrically opposed ideal cases: commensurate and incommensurate interfaces. The role of temperature is also investigated through the inclusion of a stochastic force via a Langevin molecular dynamics approach. Here, we focus on the most interesting tribological case of underdamped sliding dynamics. For different values of the chain stiffness, we evaluate the static friction threshold and consider the depinning transition mechanisms as a function of the applied driving force. As experimentally observed in QCM frictional measurements of adsorbed layers, we find that disorder operates differently depending on the starting geometrical configuration. For commensurate interfaces, randomness lowers considerably the chain depinning threshold. On the contrary, for incommensurate mating contacts, disorder favors static pinning destroying the possible frictionless (superlubric) sliding states. Interestingly, thermal and disorder effects strongly influence also the occurrence of parametric resonances inside the chain, capable of converting the kinetic energy of the center-of-mass motion into internal vibrational excitations. We comment on the nature of the different dynamical states and hysteresis (due to system bi-stability) observed at different increasing and decreasing strengths of the external force.     

Production study of high specific activity NCA Re-186g by proton and deuteron cyclotron irradiation

Very high specific activity (A_S) ^186gRe could be produced by either proton or deuteron cyclotron irradiation on highly enriched ¹⁸⁶W target in no-carrier-added (NCA) form, leading to a A_S very close to the theoretical carrier free (CF) value of 6.88 GBq μg⁻¹. Thick Target Yields (TTYs), obtained irradiating both thick metal W targets of natural isotopic composition and highly enriched powdered ¹⁸⁶W targets, were measured at different particles energies taking into account high accuracy and precision. The evaluation of radionuclidic purities of ^186gRe obtained activating highly enriched ¹⁸⁶W by both p and d were also carried out and accurately compared. The thin-target excitation functions for all Re (A = 181, 182, 183, 184, 186 and their metastable levels), and W and Ta coproduced radionuclides will be presented elsewhere in deep details.     

On the Robustness of Gaussian Elimination with Partial Pivoting

It has been recently shown that large growth factors might occur in Gaussian Elimination with Partial Pivoting (GEPP) also when solving some plausibly natural systems. In this note we argue that this potential problem could be easily solved, with much smaller risk of failure, by very small (and low cost) modifications of the basic algorithm, thus confirming its inherent robustness. To this end, we first propose an informal model with the goal of providing further support to the comprehension of the stability properties of GEPP. We then report the results of numerical experiments that confirm the viewpoint embedded in the model. Basing on the previous observations, we finally propose a simple scheme that could be turned into (even more) accurate software for the solution of linear systems.