73 research outputs found
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
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
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
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