Partial third-order quasiparticle theory: An application to the photoelectron spectrum of S-tetrazine

An alternative choice of reference state averages in electron propagator theory and retention of all self-energy terms through third-order gives rise to the partial third-order self-energy approximation, P3. Quasiparticle P3 calculations avoid the chief computational bottlenecks of third-order theory and the outer valence Green's function (OVGF). P3 requires no multiplicative factors for scaling self-energy terms and produces better accuracy than OVGF. An application to the photoelectron spectrum of s-tetrazine illustrates the ability of the P3 method to predict correct final state orderings. © 1997 John Wiley & Sons, Inc.     

Second-order shakeup terms in electron propagator calculations on F2 and H2O2

A new approximation of the electron propagator includes second-order terms in the superoperator Hamiltonian matrix that are not present in the nondiagonal, renormalized method (NR2) of J. Chem. Phys. 108 , 1008 (1998). These terms are not difficult to calculate and resemble expressions obtained with various propagator and coupled-cluster formalisms. Their inclusion produces larger, more accurate vertical ionization energies of F₂ and H₂O₂. Cancellations between the second-order terms considered here and the first-order terms present in the NR2 method reduce the importance of shakeup operators in describing the first few cationic states of these molecules. Dyson orbitals for ²A final states of H₂O₂ exhibit qualitatively important mixings between canonical orbitals. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 175–182, 1998     

Guest‐Assisted Proton Conduction in the Sulfonic Mesoporous MIL‐101 MOF

Post‐synthesis modification of MIL‐101(Cr)‐NO₂ was explored in order to decorate the organic backbone by propyl‐sulfonic groups, with the aim to incorporate mobile and acidic protons for solid‐state proton electrolyte applications. The resulting solid switched from insulating towards proton superconductive behavior under humidity, while the conductivity recorded at 363 K and 95 % relative humidity reached 4.8×10^?3 S cm^?1. Propitiously, the impregnation of the material by strong acidic molecules (H₂SO₄) further boosted the proton conductivity performances up to the remarkable σ value of 1.3×10^?1 S cm^?1 at 363 K/95 % RH, which reaches the performances of the best proton conductive MOF reported so far.     

Scalar Field in the Bianchi I: Noncommutative Classical and Quantum Cosmology

Using the ADM formalism in the minisuperspace, we obtain the commutative and noncommutative exact classical solutions and exact wave function to the Wheeler-DeWitt equation with an arbitrary factor ordering, for the anisotropic Bianchi type I cosmological model, coupled to a scalar field, cosmological term and barotropic perfect fluid. We introduce noncommutative scale factors, considering that all minisuperspace variables q ⁱ do not commute, so the symplectic structure was modified. In the classical regime, it is shown that the anisotropic parameter β _±nc and the field φ, for some value in the λ _eff cosmological term and noncommutative θ parameter, present a dynamical isotropization up to a critical cosmic time t _c ; after this time, the effects of isotropization in the noncommutative minisuperspace seems to disappear. In the quantum regimen, the probability density presents a new structure that corresponds to the value of the noncommutativity parameter.     

Γ-convergence of Variational Integrators for Constrained Systems

For a physical system described by a motion in an energy landscape under holonomic constraints, we study the Γ-convergence of variational integrators to the corresponding continuum action functional and the convergence properties of solutions of the discrete Euler–Lagrange equations to stationary points of the continuum problem. This extends the results in Müller and Ortiz (J. Nonlinear Sci. 14:279–296, 2004) to constrained systems. The convergence result is illustrated with examples of mass point systems and flexible multibody dynamics.      

Spacer-mediated synthesis of contra-thermodynamic spiroacetals: stereoselective synthesis of C2-symmetric difructose dianhydrides

The xylylene moiety (ortho, meta, and para) was employed as a rigid tether in the spacer-mediated synthesis of difructose dianhydrides (DFAs), a unique class of bis-spiroacetal derivatives present in food products. The synthetic methodology exploits the suitability of triflic acid to promote spirocyclization in organic solvents under irreversible reaction conditions, using anomeric isopropylidene fructose derivatives as precursors. Advantage was taken of the strong dependence of the conformational properties of DFAs on the relative configuration of the spiroketal centers. Highly stereoselective syntheses of the contra-thermodynamic difructofuranose and difructopyranose diastereomers, namely the C2-symmetric derivatives having the beta-configuration at both anomeric centers, have been accomplished by judicious choice of the xylylene positional isomer and of the linking position to the fructose building blocks. Interestingly, the rigid spacer concept has also been implemented to favor intermolecular processes leading to higher macrocyclic architectures that incorporate the bis-spiro fructodisaccharide subunit.     

Robust regression techniques A useful alternative for the detection of outlier data in chemical analysis

The validation of an analytical procedure means the evaluation of some performance criteria such as accuracy, sensitivity, linear range, capability of detection, selectivity, calibration curve, etc. This implies the use of different statistical methodologies, some of them related with statistical regression techniques, which may be robust or not. The presence of outlier data has a significant effect on the determination of sensitivity, linear range or capability of detection amongst others, when these figures of merit are evaluated with non-robust methodologies.In this paper some of the robust methods used for calibration in analytical chemistry are reviewed: the Huber M-estimator; the Andrews, Tukey and Welsh GM-estimators; the fuzzy estimators; the constrained M-estimators, CM; the least trimmed squares, LTS. The paper also shows that the mathematical properties of the least median squares (LMS) regression can be of great interest in the detection of outlier data in chemical analysis. A comparative analysis is made of the results obtained by applying these regression methods to synthetic and real data. There is also a review of some applications where this robust regression works in a suitable and simple way that proves very useful to secure an objective detection of outliers. The use of a robust regression is recommended in ISO 5725-5.     

Optimal Scaling in Solids Undergoing Ductile Fracture by Crazing

We derive optimal scaling laws for the macroscopic fracture energy of polymers failing by crazing. We assume that the effective deformation-theoretical free-energy density is additive in the first and fractional deformation-gradients, with zero growth in the former and linear growth in the latter. The specific problem considered concerns a material sample in the form of an infinite slab of finite thickness subjected to prescribed opening displacements on its two surfaces. For this particular geometry, we derive optimal scaling laws for the dependence of the specific fracture energy on cross-sectional area, micromechanical parameters, opening displacement and intrinsic length of the material. In particular, the upper bound is obtained by means of a construction of the crazing type.     

Advantages of a programmed temperature vaporizer inlet and parallel factor analysis in the determination of triazines in the presence of non-intentionally added substances by gas chromatography

Non-intentionally added substances (NIASs) are usually detected by acquiring mass spectra in full scan mode and then identifying the compounds corresponding to the unexpected peaks. High-resolution mass spectrometry detectors are frequently used, but this does not solve the problem that an NIAS can contribute to the abundance at m/z ratios that correspond to the fragmentation of other molecules. This problem leads to false negatives when identifying compounds, even in target analysis when the maximum permitted tolerances for relative ion abundances (SANCO/10684/2009) are taken into account. In this work, the introduction of different volumes of a test sample onto a GC/MS system that has a programmed temperature vaporizer inlet and is operating in full scan mode provides a data tensor. The proposed approach consists of considering the structure of the matrix of abundances of K m/z ratios acquired at J elution times for each chromatographic peak. Upon concatenating I of such matrices, a three-way tensor X is obtained, which is then decomposed using parallel factor analysis into as many factors as there are substances coeluting, thus providing the mass spectrum and the chromatographic profile for each of them. If the amount of an analyte changes significantly during the I injections, then it can be unequivocally identified. This procedure thus identifies coeluting NIASs, provides information about their mass spectra, and guarantees the identification and quantification of target compounds. In this work, it is used to determine five triazines in the presence of NIASs which match some of the m/z ratios of the triazines and coelute with them. Decision limits (CCα) of between 7.5 and 25.0 μg L(-1) were obtained.