Numerically inspired new version of degenerate Rayleigh-Schrödinger perturbation theory

A new form of the degenerate perturbation series is proposed. Its construction is inspired by the standard numerical algorithm of inverse iterations: As input, we only assume knowledge of an approximate non-diagonal propagator matrix at some trial zero-order energy. The convergence and a few other technicalities are illustrated by the anharmonic oscillator.Dedicated to Ladislav Trlifaj on the occasion of his 65th birthday.     

Determination of chromium in the surface nano-layer covering the Zn-based anti corrosion coating of steel sheets using a laser-induced breakdown spectrometry

A method was proposed for the determination of Cr in a thin surface nanolayer deposited on top of a micrometrical Zn-based anticorrosive coating of steel sheets using laser-induced breakdown spectrometry (LIBS). Optimization of the LIBS parameters was performed with respect to the statistical parameters of regression, these being the coefficient of determination (R ²), akaike information criterion and mean-squared prediction error. These were calculated for curves describing the relationship between the Cr surface concentration and the intensity of LIBS signal. The most critical parameter of analysis appears to be the focal spot diameter. When its value was 200 μm and corresponding energy density (fluence) had value of 413.8 J/cm², the intensity–concentration relationship revealed a negative slope. This phenomenon was caused by the difference in total ablated volume for samples with a different content of Cr in the surface layer. This phenomenon was not observed for higher values of the focal spot diameter (400 and 500 μm) and lower values of fluence (103.5 and 66.2 J/cm²). A range of calibration obtained under optimal conditions (focal spot diameter of 400 μm; single pulse mode, laser pulse energy of 130 mJ) was 11–21 mg/m² and the limit of detection was 0.7 mg/m². The recovery values calculated from the results of the proposed LIBS method and the standard ED XRF method ranged from 99.2 to 101%.     

Analysis of a combined barycentric finite volume—nonconforming finite element method for nonlinear convection-diffusion problems

We present the convergence analysis of an efficient numerical method for the solution of an initial-boundary value problem for a scalar nonlinear conservation law equation with a diffusion term. Nonlinear convective terms are approximated with the aid of a monotone finite volume scheme considered over the finite volume barycentric mesh, whereas the diffusion term is discretized by piecewise linear nonconforming triangular finite elements. Under the assumption that the triangulations are of weakly acute type, with the aid of the discrete maximum principle, a priori estimates and some compactness arguments based on the use of the Fourier transform with respect to time, the convergence of the approximate solutions to the exact solution is proved, provided the mesh size tends to zero.     

The Thermodynamic Driving Force for Kinetics in General and Enzyme Kinetics in Particular

The thermodynamic driving force of a reaction is usually taken as the chemical potential difference between products and reactants. The forward and backward reaction rates are then related to this force. This procedure is of very limited validity, as the resulting expression contains no kinetic factor and gives little information on reaction kinetics. The transformation of the reaction rate as a function of concentration (and temperature) into a function of chemical potential should be more properly performed, as illustrated by a simple example of an enzymatic reaction. The proper thermodynamic driving force is the difference between the exponentials of the totaled chemical potentials of reactants and products.     

Laser ablation of AgSbS2 and cluster analysis by time‐of‐flight mass spectrometry

Thin films of AgSbS₂ are important for phase‐change memory applications. This solid is deposited by various techniques, such as metal organic chemical vapour deposition or laser ablation deposition, and the structure of AgSbS₂(s), as either amorphous or crystalline, is already well characterized. The pulsed laser ablation deposition (PLD) of solid AgSbS₂ is also used as a manufacturing process. However, the processes in plasma have not been well studied. We have studied the laser ablation of synthesized AgSbS₂(s) using a nitrogen laser of 337 nm and the clusters formed in the laser plume were identified. The ablation leads to the formation of various single charged ternary Ag_pSb_qS_r clusters. Negatively charged AgSbS, AgSb₂S, AgSb₂S, AgSb₂S and positively charged ternary AgSbS⁺, AgSb₂S⁺, AgSb₂S, AgSb₂S clusters were identified. The formation of several singly charged Ag⁺, Ag, Ag, Sb, Sb, S ions and binary Ag_pS_r clusters such as AgSb, Ag₃S^?, SbS (r = 1–5), Sb₂S^?, Sb₂S, Sb₃S (r = 1–4) and AgS, SbS⁺, SbS, Sb₂S⁺, Sb₂S, Sb₃S (r = 1–4), AgSb was also observed. The stoichiometry of the clusters was determined via isotopic envelope analysis and computer modeling. The relation of the composition of the clusters to the crystal structure of AgSbS₂ is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Universal linear-optical quantum device: experimental implementation

We report on a linear-optical realization of a universal quantum device working with polarization encoded quantum bits. It can serve as a two-qubit partial SWAP entangling gate. The same device can be used also for filtering symmetric and antisymmetric parts of the input two-photon state. Through a partial symmetrization, the universal asymmetric quantum cloning of single-photon polarization states can be achieved. All functions can be implemented in one setup by changing the classical parameters like the phase shift and attenuation only. For the characterization of the device, the reconstruction of the output state by full process tomography was performed.     

Direct determination of cadmium in urine by electrothermal atomic absorption spectrometry after in situ electrodeposition

Determination of cadmium in urine by ETAAS suffers from severe interferences deteriorating the precision and accuracy of the analysis. Electrodeposition step prior to ETAAS allows to avoid interferences and makes cadmium determination possible even at ultratrace levels. The proposed procedures involve electrolytic deposition of cadmium from acidified urine on previously electrolytically deposited palladium film on a graphite atomizer tube, followed by removal of residual solution, pyrolysis and atomization. Both electrodeposition processes take place in a drop of the respective solution (palladium nitrate modifier and acidified urine, respectively), when Pt/Ir dosing capillary serves as an anode and the graphite tube represents a cathode. The voltage is held at −3.0 V. Matrix removal is then accomplished by withdrawal of the depleted sample solution from the tube (procedure A) or the same but followed by rinsing of the deposit with 0.2 mol l⁻¹ HNO₃ (procedure B). The accuracy of both procedures was verified by recovery test. Detection limits 0.025 and 0.030 μg Cd/l of urine were achieved for A and B procedures, respectively. Both procedures are time consuming. The measurement cycle represents 5 and 7 min for A and B procedures, respectively.