La dispersió Møller i els inicis de l’electrodinàmica quàntica: treball de recerca per al mestratge en Història de les Ciències

S’hi analitza la deducció teòrica i la contrastació experimental originals de la dispersió electró-electró (dispersió Møller, 1932), amb l’objectiu d’esbrinar quin paper van tenir en el desenvolupament de l’electrodinàmica quàntica. S’hi mostra que Christian Møller (1904-1980) va deduir la fórmula que du el seu nom mitjançant la noció de correspondència, evitant així els problemes que plantejava una incipient teoria quàntica de camps. La fórmula només va assolir el seu estatus actual d’aplicació paradigmàtica de l’electrodinàmica quàntica després de la Segona Guerra Mundial, un cop la teoria va haver superat aquests problemes a través del procés de renormalització. El treball aclareix d’aquesta manera un episodi clau en el desenvolupament d’una de les teories fonamentals de la física del segle XX.

Second-order Møller-Plesset perturbation theory without basis set superposition error : II : open-shell systems

The basis set superposition error-free second-order MØller-Plesset perturbation theory of intermolecular interactions was studied. The difficulties of the counterpoise (CP) correction in open-shell systems were also discussed. The calculations were performed by a program which was used for testing the new variants of the theory. It was shown that the CP correction for the diabatic surfaces should be preferred to the adiabatic ones

Lower bounds for kernelizations

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Strong isomorphism reductions in complexity theory

We give the first systematic study of strong isomorphism reductions, a notion of reduction more appropriate than polynomial time reduction when, for example, comparing the computational complexity of the isomorphim problem for different classes of structures. We show that the partial ordering of its degrees is quite rich. We analyze its relationship to a further type of reduction between classes of structures based on purely comparing for every n the number of nonisomorphic structures of cardinality at most n in both classes. Furthermore, in a more general setting we address the question of the existence of a maximal element in the partial ordering of the degrees.

Consistency and optimality

Assume that the problem Qo is not solvable in polynomial time. For theories T containing a sufficiently rich part of true arithmetic we characterize T U {ConT} as the minimal extension of T proving for some algorithm that it decides Qo as fast as any algorithm B with the property that T proves that B decides Qo. Here, ConT claims the consistency of T. Moreover, we characterize problems with an optimal algorithm in terms of arithmetical theories.

Hard instances of algorithms and proof systems

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El Cinema cru : influència del fenomen audiovisual global-popular en el cinema del canvi de mil·leni

El Cru són les formes d'expressió de procedència no professional que combinen so i imatge en moviment i que, a partir de principis de la dècada dels 90 del sègle XX i pel context històric de l'època, estan a l'abast d'una part significativa i creixent de la població mundial, amb una també creixent potencialitat de difusió massiva a escala planetària, el que dota al conjunt d'una visibilitat en augment en la societat i el torna, en conseqüència, un referent ineludible. Erigit el Cru com un referent cada vegada més important en la nostre societat, trobem lògic pensar que el cinema realitzat per a la seva projecció a sales d'exhibició, hagi pogut veure-s'hi influenciat. El present treball de recerca pretén demostrar i analitzar aquesta influència del Cru en el cinema del canvi de mil•lenni

Quantifying rock fabrics: a test of autocorrelation of the spatial distribution of cristals

A novel test of spatial independence of the distribution of crystals or phases in rocksbased on compositional statistics is introduced. It improves and generalizes the commonjoins-count statistics known from map analysis in geographic information systems.Assigning phases independently to objects in RD is modelled by a single-trial multinomialrandom function Z(x), where the probabilities of phases add to one and areexplicitly modelled as compositions in the K-part simplex SK. Thus, apparent inconsistenciesof the tests based on the conventional joins{count statistics and their possiblycontradictory interpretations are avoided. In practical applications we assume that theprobabilities of phases do not depend on the location but are identical everywhere inthe domain of de nition. Thus, the model involves the sum of r independent identicalmultinomial distributed 1-trial random variables which is an r-trial multinomialdistributed random variable. The probabilities of the distribution of the r counts canbe considered as a composition in the Q-part simplex SQ. They span the so calledHardy-Weinberg manifold H that is proved to be a K-1-affine subspace of SQ. This isa generalisation of the well-known Hardy-Weinberg law of genetics. If the assignmentof phases accounts for some kind of spatial dependence, then the r-trial probabilitiesdo not remain on H. This suggests the use of the Aitchison distance between observedprobabilities to H to test dependence. Moreover, when there is a spatial uctuation ofthe multinomial probabilities, the observed r-trial probabilities move on H. This shiftcan be used as to check for these uctuations. A practical procedure and an algorithmto perform the test have been developed. Some cases applied to simulated and realdata are presented.Key words: Spatial distribution of crystals in rocks, spatial distribution of phases,joins-count statistics, multinomial distribution, Hardy-Weinberg law, Hardy-Weinbergmanifold, Aitchison geometry

Basis set superposition error-counterpoise corrected potential energy surfaces : application to hydrogen peroxide ... X (X=F-, Cl-, Br-, Li+, Na+) complexes

Møller-Plesset (MP2) and Becke-3-Lee-Yang-Parr (B3LYP) calculations have been used to compare the geometrical parameters, hydrogen-bonding properties, vibrational frequencies and relative energies for several X- and X+ hydrogen peroxide complexes. The geometries and interaction energies were corrected for the basis set superposition error (BSSE) in all the complexes (1-5), using the full counterpoise method, yielding small BSSE values for the 6-311 + G(3df,2p) basis set used. The interaction energies calculated ranged from medium to strong hydrogen-bonding systems (1-3) and strong electrostatic interactions (4 and 5). The molecular interactions have been characterized using the atoms in molecules theory (AIM), and by the analysis of the vibrational frequencies. The minima on the BSSE-counterpoise corrected potential-energy surface (PES) have been determined as described by S. Simón, M. Duran, and J. J. Dannenberg, and the results were compared with the uncorrected PES

The effect of counterpoise correction and relaxation energy term to the internal rotation barriers: application to the BF3 ...NH3 and C2H4 ...SO2 dimers

The relevance of the fragment relaxation energy term and the effect of the basis set superposition error on the geometry of the BF3⋯NH3 and C2H4⋯SO2 van der Waals dimers have been analyzed. Second-order Møller-Plesset perturbation theory calculations with the d95(d,p) basis set have been used to calculate the counterpoise-corrected barrier height for the internal rotations. These barriers have been obtained by relocating the stationary points on the counterpoise-corrected potential energy surface of the processes involved. The fragment relaxation energy can have a large influence on both the intermolecular parameters and barrier height. The counterpoise correction has proved to be important for these systems

C-H···O H-bonded complexes: how does basis set superposition error change their potential-energy surfaces?

Geometries, vibrational frequencies, and interaction energies of the CNH⋯O3 and HCCH⋯O3 complexes are calculated in a counterpoise-corrected (CP-corrected) potential-energy surface (PES) that corrects for the basis set superposition error (BSSE). Ab initio calculations are performed at the Hartree-Fock (HF) and second-order Møller-Plesset (MP2) levels, using the 6-31G(d,p) and D95++(d,p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy (ZPVE) and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the unconnected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary

How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?

We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using the counterpoise (CP) method. This method is applied to the H-bonding complexes HF/HCN, HF/H2O, and HCCH/H2O using the 6-31G(d,p) and D95 + + (d,p) basis sets at both the Hartree-Fock and second-order Møller-Plesset levels. We report the interaction energies, geometries, and vibrational frequencies of these complexes on the CP-optimized surfaces; and compare them with similar values calculated using traditional methods, including the (more traditional) single point CP correction. Upon optimization on the CP-corrected surface, the interaction energies become more negative (before vibrational corrections) and the H-bonding stretching vibrations decrease in all cases. The extent of the effects vary from extremely small to quite large depending on the complex and the calculational method. The relative magnitudes of the vibrational corrections cannot be predicted from the H-bond stretching frequencies alone