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

Counterpoise-corrected geometries and harmonic frequencies of N-body clusters: application to (HF)n (n=3,4)

A study was conducted on the methods of basis set superposition error (BSSE)-free geometry optimization and frequency calculations in clusters larger than a dimer. In particular, three different counterpoise schemes were critically examined. It was shown that the counterpoise-corrected supermolecule energy can be easily obtained in all the cases by using the many-body partitioning of energy

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

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Dynamical Systems approach to Saffman-Taylor fingering. A Dynamical Solvability Scenario

A dynamical systems approach to competition of Saffman-Taylor fingers in a Hele-Shaw channel is developed. This is based on global analysis of the phase space flow of the low-dimensional ordinary-differential-equation sets associated with the classes of exact solutions of the problem without surface tension. Some simple examples are studied in detail. A general proof of the existence of finite-time singularities for broad classes of solutions is given. Solutions leading to finite-time interface pinchoff are also identified. The existence of a continuum of multifinger fixed points and its dynamical implications are discussed. We conclude that exact zero-surface tension solutions taken in a global sense as families of trajectories in phase space are unphysical because the multifinger fixed points are nonhyperbolic, and an unfolding does not exist within the same class of solutions. Hyperbolicity (saddle-point structure) of the multifinger fixed points is argued to be essential to the physically correct qualitative description of finger competition. The restoring of hyperbolicity by surface tension is proposed as the key point to formulate a generic dynamical solvability scenario for interfacial pattern selection.

The statistical accuracy of surveys on business and economic perspectives: a case study

In this paper, we develop a new decision making model and apply it in political Surveys of economic climate collect opinions of managers about the short-term future evolution of their business. Interviews are carried out on a regular basis and responses measure optimistic, neutral or pessimistic views about the economic perspectives. We propose a method to evaluate the sampling error of the average opinion derived from a particular type of survey data. Our variance estimate is useful to interpret historical trends and to decide whether changes in the index from one period to another are due to a structural change or whether ups and downs can be attributed to sampling randomness. An illustration using real data from a survey of business managers opinions is discussed.

The Quaternary Active Faults Database of Iberia (QAFI v.2.0)

The Quaternary Active Faults Database of Iberia (QAFI) is an initiative lead by the Institute of Geology and Mines of Spain (IGME) for building a public repository of scientific data regarding faults having documented activity during the last 2.59 Ma (Quaternary). QAFI also addresses a need to transfer geologic knowledge to practitioners of seismic hazard and risk in Iberia by identifying and characterizing seismogenic fault-sources. QAFI is populated by the information freely provided by more than 40 Earth science researchers, storing to date a total of 262 records. In this article we describe the development and evolution of the database, as well as its internal architecture. Aditionally, a first global analysis of the data is provided with a special focus on length and slip-rate fault parameters. Finally, the database completeness and the internal consistency of the data are discussed. Even though QAFI v.2.0 is the most current resource for calculating fault-related seismic hazard in Iberia, the database is still incomplete and requires further review.

Factores de explotación asociados a la duración del anestro postparto en vacas nodrizas de razas Parda de Montaña y Pirenaica

Para determinar los factores de explotación relacionados con la reactivación ovárica postparto en vacas nodrizas se realizó un análisis global de una serie de indicadores productivos y la duración del anestro postparto (APP) de 549 vacas explotadas en condiciones extensivas. Debido a la naturaleza multifactorial del proceso en estudio se eligió la metodología estadística multivariante (Análisis Factorial de Correspondencias Múltiples y Análisis Cluster). La duración del APP estuvo asociada a cuatro factores que explicaron el 59% de la heterogeneidad inicial de la muestra y que se definieron como: «Alimentación preparto» (19% de la inercia), «Alimentación postparto-Edad» (16.4%), «Manejo del ternero» (13%) y «Dificultad al parto» (10.5%). Estos factores se introdujeron en un Análisis Cluster que identificó cinco grupos de vacas con características productivas y reproductivas diferentes, y que denominamos como: «Primíparas», «Acceso restringido», «Acceso Libre-Parda de Montaña», «Parto de otoño» y «Parto de primavera». La raza no estuvo relacionada con la duración del APP, aunque el análisis Cluster asoció los largos APP inducidos por la crianza libre con la raza Parda de Montaña. En la raza Parda de Montaña, la duración del APP fue mayor en primavera que en otoño debido a diferencias nutricionales más que a un efecto estacional en sí. El parto de otoño se adaptó mejor a las condiciones de montaña seca.

Different Plasma Markers of Inflammation Are Influenced by Immune Recovery and cART Composition or Intensification in Treated HIV Infected Individuals

Abstract Background HIV-1 infection increases plasma levels of inflammatory markers. Combination antiretroviral therapy (cART) does not restore inflammatory markers to normal levels. Since intensification of cART with raltegravir reduced CD8 T-cell activation in the Discor-Ral and IntegRal studies, we have evaluated the effect of raltegravir intensification on several soluble inflammation markers in these studies. Methods Longitudinal plasma samples (0–48 weeks) from the IntegRal (n = 67, 22 control and 45 intensified individuals) and the Discor-Ral studies (44 individuals with CD4 T-cell counts<350 cells/µl, 14 control and 30 intensified) were assayed for 25 markers. Mann-Whitney, Wilcoxon, Spearman test and linear mixed models were used for analysis. Results At baseline, different inflammatory markers were strongly associated with HCV co-infection, lower CD4 counts and with cART regimens (being higher in PI-treated individuals), but poorly correlated with detection of markers of residual viral replication. Although raltegravir intensification reduced inflammation in individuals with lower CD4 T-cell counts, no effect of intensification was observed on plasma markers of inflammation in a global analysis. An association was found, however, between reductions in immune activation and plasma levels of the coagulation marker D-dimer, which exclusively decreased in intensified patients on protease inhibitor (PI)-based cART regimens (P = 0.040). Conclusions The inflammatory profile in treated HIV-infected individuals showed a complex association with HCV co-infection, the levels of CD4 T cells and the cART regimen. Raltegravir intensification specifically reduced D-dimer levels in PI-treated patients, highlighting the link between cART composition and residual viral replication; however, raltegravir had little effect on other inflammatory markers.

Calculation of the variance in surveys of the economic climate

Public opinion surveys have become progressively incorporated into systems of official statistics. Surveys of the economic climate are usually qualitative because they collect opinions of businesspeople and/or experts about the long-term indicators described by a number of variables. In such cases the responses are expressed in ordinal numbers, that is, the respondents verbally report, for example, whether during a given trimester the sales or the new orders have increased, decreased or remained the same as in the previous trimester. These data allow to calculate the percent of respondents in the total population (results are extrapolated), who select every one of the three options. Data are often presented in the form of an index calculated as the difference between the percent of those who claim that a given variable has improved in value and of those who claim that it has deteriorated.

SQualTrack: A Tool for Robust Fault Detection

One of the techniques used to detect faults in dynamic systems is analytical redundancy. An important difficulty in applying this technique to real systems is dealing with the uncertainties associated with the system itself and with the measurements. In this paper, this uncertainty is taken into account by the use of intervals for the parameters of the model and for the measurements. The method that is proposed in this paper checks the consistency between the system's behavior, obtained from the measurements, and the model's behavior; if they are inconsistent, then there is a fault. The problem of detecting faults is stated as a quantified real constraint satisfaction problem, which can be solved using the modal interval analysis (MIA). MIA is used because it provides powerful tools to extend the calculations over real functions to intervals. To improve the results of the detection of the faults, the simultaneous use of several sliding time windows is proposed. The result of implementing this method is semiqualitative tracking (SQualTrack), a fault-detection tool that is robust in the sense that it does not generate false alarms, i.e., if there are false alarms, they indicate either that the interval model does not represent the system adequately or that the interval measurements do not represent the true values of the variables adequately. SQualTrack is currently being used to detect faults in real processes. Some of these applications using real data have been developed within the European project advanced decision support system for chemical/petrochemical manufacturing processes and are also described in this paper

Analysis and optimization of the satellite-to-plane link of an aeronautical global system

En aquest projecte s’ha analitzat i optimitzat l’enllaç satèl·lit amb avió per a un sistema aeronàutic global. Aquest nou sistema anomenat ANTARES està dissenyat per a comunicar avions amb estacions base mitjançant un satèl·lit. Aquesta és una iniciativa on hi participen institucions oficials en l’aviació com ara l’ECAC i que és desenvolupat en una col·laboració europea d’universitats i empreses. El treball dut a terme en el projecte compren bàsicament tres aspectes. El disseny i anàlisi de la gestió de recursos. La idoneïtat d’utilitzar correcció d’errors en la capa d’enllaç i en cas que sigui necessària dissenyar una opció de codificació preliminar. Finalment, estudiar i analitzar l’efecte de la interferència co-canal en sistemes multifeix. Tots aquests temes són considerats només per al “forward link”. L’estructura que segueix el projecte és primer presentar les característiques globals del sistema, després centrar-se i analitzar els temes mencionats per a poder donar resultats i extreure conclusions.

The global report of trafficking in persons: analysis and results

L'Oficina de les Nacions Unides contra la Droga i el Delicte en el seu informe "Global Report on Trafficking in Persons" de 2012 recull que "l'explotació sexual és, amb gran diferència, la forma de tràfic de persones detectades amb més freqüència, concretament en xifres un total del 79 % dels casos. Enllaç a l'informe sencer: http://www.unodc.org/documents/data-and-analysis/glotip/Trafficking_in_Persons_2012_web.pdf