The Dual-Phase Mechanism for the Catalytic Conversion of n-Butane to Maleic Anhydride by the Vanadyl Pyrophosphate Heterogeneous Catalyst

Industrial production of maleic anhydride (MA) from n-butane relies on the vanadyl pyrophosphate (VPO) catalyst. Improving VPO’s selectivity and activity could have enormous economic and environmental impact, but efforts have been impeded by uncertainties regarding the active phases and atomistic mechanism of the VPO catalyst. We report here a plausible 15-step mechanism taking n-butane to MA with energetics computed using hybrid density functional theory calculations on periodic models of the surface layers. We find that the P═O group on the X1 phase is solely responsible for butane activation. The P═O group is made active by the reduction of a nearby vanadium atom, a so-called reduction-coupled oxo-activation. However, we show that a catalyst consisting only of the X1 phase would not be selective because of several highly exothermic steps. Instead, we show that the more stable α1 phase can catalyze the formation of MA after initial activation, thus proposing and validating a dual-phase mechanism that takes butane to MA. Our new mechanism inspires the development of a more selective VPO catalyst containing small X1 regions highly separated by α_1 surfaces

Asymptotic behaviour in temporal logic

International audienceno abstrac

BTZ Black Hole with Gravitational Chern-Simons: Thermodynamics and Statistical Entropy

Recently, the BTZ black hole in the presence of the gravitational Chern-Simons (GCS) term has been studied and it has been found that the usual thermodynamical quantities, like as the black hole mass, angular momentum, and black hole entropy, are modified. But, for large values of the GCS coupling, where the modification terms dominate the original terms, some exotic behaviors occur, like as the roles of the mass and angular momentum are interchanged and the black hole entropy depends more on the $inner$-horizon area than the outer one. A basic physical problem of this system is that the form of entropy does not guarantee the second law of thermodynamics, in contrast to the Bekenstein-Hawking (BH) entropy. Moreover, this entropy does $not$ agree with the statistical entropy, in contrast to a good agreement for small values of the GCS coupling. Here I find that there is another entropy formula where the usual BH form dominates the inner-horizon term again, as in the small GCS coupling, such as the second law of thermodynamics can be guaranteed. I compare the result of the holographic approach with the classical- symmetry-algebra-based approach and I find exact agreements even with the higher-derivative term of GCS. This provides a non-trivial check of the AdS/CFT-correspondence in the presence of higher-derivative terms in the gravity action.Comment: Accepted in Phys. Rev. D; Shortened version, Raised a new question of the validity of the first law (No. 5 in Sec.5), Clarified the relation with the Euclidean action approach for $1/\hbar$ factor (below (3.2)

Relations as executable specifications: taming partiality and non-determinism using invariants

Comunicação publicada em "Lecture Notes in Computer Science", vol. 7560 (2012), pag. 146-161The calculus of relations has been widely used in program specification and reasoning. It is very tempting to use such specifications as running prototypes of the desired program, but, even considering finite domains, the inherent partiality and non-determinism of relations makes this impractical and highly inefficient. To tame partiality we prescribe the usage of invariants, represented by coreflexives, to characterize the exact domains and codomains of relational specifications. Such invariants can be used as pre-condition checkers to avoid runtime errors. Moreover, we show how such invariants can be used to narrow the non-deterministic execution of relational specifications, making it viable for a relevant class of problems. In particular, we show how the proposed techniques can be applied to execute specifications of bidirectional transformations, a domain where partiality and non-determinism are paramount.Fundação para a Ciência e a Tecnologi

Relating Leptogenesis to Low Energy Flavor Violating Observables in Models with Spontaneous CP Violation

In the minimal left-right symmetric model, there are only two intrinsic CP violating phases to account for all CP violation in both the quark and lepton sectors, if CP is broken spontaneously by the complex phases in the VEV's of the scalar fields. In addition, the left- and right-handed Majorana mass terms for the neutrinos are proportional to each other due to the parity in the model. This is thus a very constrained framework, making the existence of correlations among the CP violation in leptogenesis, neutrino oscillation and neutrinoless double beta decay possible. In these models, CP violation in the leptonic sector and CP violation in the quark sector are also related. We find, however, that such connection is rather weak due to the large hierarchy in the bi-doublet VEV required by a realistic quark sector.Comment: RevTeX4, 21 pages; v2: references added, version to appear in Phys. Rev.

Quantum integrable system with two color components in two dimensions

The Davey-Stewartson 1(DS1) system[9] is an integrable model in two dimensions. A quantum DS1 system with 2 colour-components in two dimensions has been formulated. This two-dimensional problem has been reduced to two one-dimensional many-body problems with 2 colour-components. The solutions of the two-dimensional problem under consideration has been constructed from the resulting problems in one dimensions. For latters with the $\delta$-function interactions and being solved by the Bethe ansatz, we introduce symmetrical and antisymmetrical Young operators of the permutation group and obtain the exact solutions for the quantum DS1 system. The application of the solusions is discussed.Comment: 14 pages, LaTeX fil

Symmetric Textures in SO(10) and LMA Solution for Solar Neutrinos

We analyze a model based on SUSY SO(10) combined with SU(2) family symmetry and symmetric mass matrices constructed by the authors recently. Previously, only the parameter space for the LOW and vacuum oscillation (VO) solutions was investigated. We indicate in this note the parameter space which leads to large mixing angle (LMA) solution to the solar neutrino problem with a slightly modified effective neutrino mass matrix. The symmetric mass textures arising from the left-right symmetry breaking and the SU(2) symmetry breaking give rise to very good predictions for the quark and lepton masses and mixing angles. The prediction of our model for the |U_{e\nu_{3}}| element in the Maki-Nakagawa-Sakata (MNS) matrix is close to the sensitivity of current experiments; thus the validity of our model can be tested in the near future. We also investigate the correlation between the |U_{e\nu_{3}}| element and \tan^{2}\theta_{\odot} in a general two-zero neutrino mass texture.Comment: RevTeX4; 9 pages; 1 figur

Dirac Leptogenesis with a Non-anomalous U(1)′U(1)^{\prime} Family Symmetry

We propose a model for Dirac leptogenesis based on a non-anomalous $U(1)^{\prime}$ gauged family symmetry. The anomaly cancellation conditions are satisfied with no new chiral fermions other than the three right-handed neutrinos, giving rise to stringent constraints among the charges. Realistic masses and mixing angles are obtained for all fermions. The model predicts neutrinos of the Dirac type with naturally suppressed masses. Dirac leptogenesis is achieved through the decay of the flavon fields. The cascade decays of the vector-like heavy fermions in the Froggatt-Nielsen mechanism play a crucial role in the separation of the primodial lepton numbers. We find that a large region of parameter space of the model gives rise to a sufficient cosmological baryon number asymmetry through Dirac leptogenesis.Comment: 8 pages, 8 figures, version to appear in JHE

Reducing Interanalyst Variability in Photovoltaic Degradation Rate Assessments

The economic return on investment of a commercial photovoltaic system depends greatly on its performance over the long term and, hence, its degradation rate. Many methods have been proposed for assessing system degradation rates from outdoor performance data. However, comparing reported values from one analyst and research group to another requires a common baseline of performance; consistency between methods and analysts can be a challenge. An interlaboratory study was conducted involving different volunteer analysts reporting on the same photovoltaic performance data using different methodologies. Initial variability of the reported degradation rates was so high that analysts could not come to a consensus whether a system degraded or not. More consistent values are received when written guidance is provided to each analyst. Further improvements in analyst variance was accomplished by using the free open-source software RdTools, allowing a reduction in variance between analysts by more than two orders of magnitude over the first round, where multiple analysis methods are allowed. This article highlights many pitfalls in conducting 'routine' degradation analysis, and it addresses some of the factors that must be considered when comparing degradation results reported by different analysts or methods