On the energetics of P-P bond dissociation of sterically strained tetraamino-diphosphanes

The homolytic P-P bond fission in a series of sterically congested tetraaminodiphosphanes (R2N)(2)P-P-(NR2)(2) ({4}(2)-{9}(2), two of which were newly synthesized and fully characterized) into diaminophosphanyl radicals (R2N)(2)P-center dot (4-9) was monitored by VT EPR spectroscopy. Determination of the radical concentration from the EPR spectra permitted to calculate free dissociation energies Delta G(Diss)(295) as well as dissociation enthalpies Delta H-Diss and entropies Delta S-Diss, respectively. Large positive values of Delta G(Diss)(295) indicate that the degree of dissociation is in most cases low, and the concentration of persistent radicals - even if they are spectroscopically observable at ambient temperature - remains small. Appreciable dissociation was established only for the sterically highly congested acyclic derivative {9}(2). Analysis of the trends in experimental data in connection with DFT studies indicate that radical formation is favoured by large entropy contributions and the energetic effect of structural relaxation (geometrical distortions and conformational changes in acyclic derivatives) in the radicals, and disfavoured by attractive dispersion forces. Comparison of the energetics of formation for CC-saturated N-heterocyclic diphosphanes and the 7 pi-radical 3c indicates that the effect of energetic stabilization by pi-electron delocalization in the latter is visible, but stands back behind those of steric and entropic contributions. Evaluation of spectroscopic and computational data indicates that diaminophosphanyl radicals exhibit, in contrast to aminophosphenium cations, no strong energetic preference for a planar arrangement of the (R2N)(2)P unit.Peer reviewe

Torsion nonminimally coupled to the electromagnetic field and birefringence

In conventional Maxwell--Lorentz electrodynamics, the propagation of light is influenced by the metric, not, however, by the possible presence of a torsion T. Still the light can feel torsion if the latter is coupled nonminimally to the electromagnetic field F by means of a supplementary Lagrangian of the type l^2 T^2 F^2 (l = coupling constant). Recently Preuss suggested a specific nonminimal term of this nature. We evaluate the spacetime relation of Preuss in the background of a general O(3)-symmetric torsion field and prove by specifying the optical metric of spacetime that this can yield birefringence in vacuum. Moreover, we show that the nonminimally coupled homogeneous and isotropic torsion field in a Friedmann cosmos affects the speed of light.Comment: Revtex, 12 pages, no figure

Maxwell's theory on a post-Riemannian spacetime and the equivalence principle

The form of Maxwell's theory is well known in the framework of general relativity, a fact that is related to the applicability of the principle of equivalence to electromagnetic phenomena. We pose the question whether this form changes if torsion and/or nonmetricity fields are allowed for in spacetime. Starting from the conservation laws of electric charge and magnetic flux, we recognize that the Maxwell equations themselves remain the same, but the constitutive law must depend on the metric and, additionally, may depend on quantities related to torsion and/or nonmetricity. We illustrate our results by putting an electric charge on top of a spherically symmetric exact solution of the metric-affine gauge theory of gravity (comprising torsion and nonmetricity). All this is compared to the recent results of Vandyck.Comment: 9 pages, REVTeX, no figures; minor changes, version to be published in Class. Quantum Gra

Static Safety for an Actor Dedicated Process Calculus by Abstract Interpretation

The actor model eases the definition of concurrent programs with non uniform behaviors. Static analysis of such a model was previously done in a data-flow oriented way, with type systems. This approach was based on constraint set resolution and was not able to deal with precise properties for communications of behaviors. We present here a new approach, control-flow oriented, based on the abstract interpretation framework, able to deal with communication of behaviors. Within our new analyses, we are able to verify most of the previous properties we observed as well as new ones, principally based on occurrence counting

Torsion Degrees of Freedom in the Regge Calculus as Dislocations on the Simplicial Lattice

Using the notion of a general conical defect, the Regge Calculus is generalized by allowing for dislocations on the simplicial lattice in addition to the usual disclinations. Since disclinations and dislocations correspond to curvature and torsion singularities, respectively, the method we propose provides a natural way of discretizing gravitational theories with torsion degrees of freedom like the Einstein-Cartan theory. A discrete version of the Einstein-Cartan action is given and field equations are derived, demanding stationarity of the action with respect to the discrete variables of the theory

Covariance properties and regularization of conserved currents in tetrad gravity

We discuss the properties of the gravitational energy-momentum 3-form within the tetrad formulation of general relativity theory. We derive the covariance properties of the quantities describing the energy-momentum content under Lorentz transformations of the tetrad. As an application, we consider the computation of the total energy (mass) of some exact solutions of Einstein's general relativity theory which describe compact sources with asymptotically flat spacetime geometry. As it is known, depending on the choice of tetrad frame, the formal total integral for such configurations may diverge. We propose a natural regularization method which yields finite values for the total energy-momentum of the system and demonstrate how it works on a number of explicit examples.Comment: 36 pages, Revtex, no figures; small changes, published versio

Space-time defects and teleparallelism

We consider the class of space-time defects investigated by Puntigam and Soleng. These defects describe space-time dislocations and disclinations (cosmic strings), and are in close correspondence to the actual defects that arise in crystals and metals. It is known that in such materials dislocations and disclinations require a small and large amount of energy, respectively, to be created. The present analysis is carried out in the context of the teleparallel equivalent of general relativity (TEGR). We evaluate the gravitational energy of these space-time defects in the framework of the TEGR and find that there is an analogy between defects in space-time and in continuum material systems: the total gravitational energy of space-time dislocations and disclinations (considered as idealized defects) is zero and infinit, respectively.Comment: 22 pages, no figures, to appear in the Class. Quantum Gravit

Asymptotic behaviour of cylindrical waves interacting with spinning strings

We consider a family of cylindrical spacetimes endowed with angular momentum that are solutions to the vacuum Einstein equations outside the symmetry axis. This family was recently obtained by performing a complete gauge fixing adapted to cylindrical symmetry. In the present work, we find boundary conditions that ensure that the metric arising from this gauge fixing is well defined and that the resulting reduced system has a consistent Hamiltonian dynamics. These boundary conditions must be imposed both on the symmetry axis and in the region far from the axis at spacelike infinity. Employing such conditions, we determine the asymptotic behaviour of the metric close to and far from the axis. In each of these regions, the approximate metric describes a conical geometry with a time dislocation. In particular, around the symmetry axis the effect of the singularity consists in inducing a constant deficit angle and a timelike helical structure. Based on these results and on the fact that the degrees of freedom in our family of metrics coincide with those of cylindrical vacuum gravity, we argue that the analysed set of spacetimes represent cylindrical gravitational waves surrounding a spinning cosmic string. For any of these spacetimes, a prediction of our analysis is that the wave content increases the deficit angle at spatial infinity with respect to that detected around the axis.Comment: 25 pages, accepted for publication in Classical and Quantum Gravit