A case study in ultracold reactive scattering: D + H2

We report theoretical results for reaction and vibrational quenching of the ultracold collision D + H(2) (v, j = 0) for a wide range of initial vibrationally excited states v. The v-dependence of the zero-temperature limit of the reaction rate coefficient shows two distinct regimes: a barrier dominated regime for 0 ≤ v ≤ 4, and a barrierless regime for v ≥ 5. We also present detailed distributions over the rovibrational states of the products. We find an approximate conservation of the internal vibrational energy; namely, the branching ratios always favor the highly excited final states, which have vibrational energies similar to that of the entrance channel.     

Asymptotic equivalence between Cournot–Nash and Walras equilibria in exchange economies with atoms and an atomless part

In this paper, we consider an exchange economy à la Shitovitz (Econometrica 41:467–501, 1973), with atoms and an atomless set. We associate with it a strategic market game of the kind first proposed by Lloyd S. Shapley, known as the Shapley window model. We analyze the relationship between the set of the Cournot–Nash allocations of the strategic market game and the Walras allocations of the exchange economy with which it is associated. We show, with an example, that even when atoms are countably infinite, any Cournot–Nash allocation of the game is not a Walras allocation of the underlying exchange economy. Accordingly, in the original spirit of Cournot (Recherches sur les principes mathématiques de la théorie des richesses. Hachette, Paris, 1838), we partially replicate the mixed exchange economy by increasing the number of atoms, without affecting the atomless part, and ensuring that the measure space of agents remains finite. Our main theorem shows that any sequence of Cournot–Nash allocations of the strategic market games associated with the partial replications of the exchange economy has a limit point for each trader and that the assignment determined by these limit points is a Walrasian allocation of the original economy.     

A time-dependent wave packet study of the vibronic and spin-orbit interactions in the dynamics of Cl((2)P)+H(2)-->HCl(X (1)Sigma(g) (+))+H((2)S) reaction

We investigate the vibronic and spin-orbit (SO) coupling effects in the state-selected dynamics of the title reaction with the aid of a time-dependent wave packet approach. The ab initio potential energy surfaces of Capecchi and Werner [Science 296, 715 (2002)] have been employed for this purpose. Collinear approach of the Cl((2)P) atom to the H(2) molecule splits the degeneracy of the (2)P state and gives rise to (2)Sigma and (2)Pi electronic states. These two surfaces form a conical intersection at this geometry. These states transform as 1 (2)A('), 1 (2)A("), and 2 (2)A('), respectively, at the nonlinear configurations of the nuclei. In addition, the SO interaction due to Cl atom further splits these states into (2)Sigma(1/2), (2)Pi(3/2), and (2)Pi(1/2) components at the linear geometry. The ground-state reagent Cl((2)P(3/2))+H(2) correlates with (2)Sigma(1/2) and (2)Pi(3/2), where as the SO excited reagent Cl(*)((2)P(1/2))+H(2) correlates with (2)Pi(1/2) at the linear geometry. In order to elucidate the impact of the vibronic and SO coupling effects on the initial state-selected reactivity of these electronic states we carry out quantum scattering calculations based on a flux operator formalism and a time-dependent wave packet approach. In this work, total reaction probabilities and the time dependence of electronic population of the system by initiating the reaction on each of the above electronic states are presented. The role of conical intersection alone on the reaction dynamics is investigated with a coupled two-state model and for the total angular momentum J=0 (neglecting the electronic orbital angular momentum) both in a diabatic as well as in the adiabatic electronic representation. The SO interaction is then included and the dynamics is studied with a coupled three-state model comprising six diabatic surfaces for the total angular momentum J=0.5 neglecting the Coriolis Coupling terms of the Hamiltonian. Companion calculations are carried out for the uncoupled adiabatic and diabatic surfaces in order to explicitly reveal the impact of two different surface coupling mechanisms in the dynamics of this prototypical reaction.     

A retention‐time‐shift‐tolerant background subtraction and noise reduction algorithm (BgS‐NoRA) for extraction of drug metabolites in liquid chromatography/mass spectrometry data from biological matrices

A retention‐time‐shift‐tolerant background subtraction and noise reduction algorithm (BgS‐NoRA) is implemented using the statistical programming language R to remove non‐drug‐related ion signals from accurate mass liquid chromatography/mass spectrometry (LC/MS) data. The background‐subtraction part of the algorithm is similar to a previously published procedure (Zhang H and Yang Y. J. Mass Spectrom. 2008, 43: 1181–1190). The noise reduction algorithm (NoRA) is an add‐on feature to help further clean up the residual matrix ion noises after background subtraction. It functions by removing ion signals that are not consistent across many adjacent scans. The effectiveness of BgS‐NoRA was examined in biological matrices by spiking blank plasma extract, bile and urine with diclofenac and ibuprofen that have been pre‐metabolized by microsomal incubation. Efficient removal of background ions permitted the detection of drug‐related ions in in vivo samples (plasma, bile, urine and feces) obtained from rats orally dosed with ¹⁴C‐loratadine with minimal interference. Results from these experiments demonstrate that BgS‐NoRA is more effective in removing analyte‐unrelated ions than background subtraction alone. NoRA is shown to be particularly effective in the early retention region for urine samples and middle retention region for bile samples, where the matrix ion signals still dominate the total ion chromatograms (TICs) after background subtraction. In most cases, the TICs after BgS‐NoRA are in excellent qualitative correlation to the radiochromatograms. BgS‐NoRA will be a very useful tool in metabolite detection and identification work, especially in first‐in‐human (FIH) studies and multiple dose toxicology studies where non‐radio‐labeled drugs are administered. Data from these types of studies are critical to meet the latest FDA guidance on Metabolite in Safety Testing (MIST). Copyright © 2009 John Wiley & Sons, Ltd.     

Information entropic measures of a quantum harmonic oscillator in symmetric and asymmetric confinement within an impenetrable box

Information‐based uncertainty measures like Shannon entropy, Onicescu energy and Fisher information (in position and momentum space) are employed to understand the effect of symmetric and asymmetric confinement in a quantum harmonic oscillator. Also, the transformation of the Hamiltonian into a dimensionless form gives an idea of the composite effect of force constant and confinement length (x_c). In the symmetric case, a wide range of x_c has been taken up, whereas asymmetric confinement is dealt with by shifting the minimum of the potential from the origin keeping box length and boundary fixed. Eigenvalues and eigenvectors for these systems are obtained quite accurately via an imaginary‐time propagation scheme. For asymmetric confinement, a variation‐induced exact diagonalization procedure is also introduced, which produces very high quality results. One finds that, in symmetric confinement, after a certain characteristic x_c, all these properties converge to respective values of a free harmonic oscillator. In the asymmetric situation, excited‐state energies always pass through a maximum. For this potential, the classical turning point decreases, whereas well depth increases with the strength of asymmetry. A study of these uncertainty measures reveals that localization increases with an increase of the asymmetry parameter.

     

Synthesis and surface modified hard magnetic properties in Co0.5Pt0.5 nanocrystallites from a rheological liquid precursor

Small crystallites of a metastable phase Co_0.5Pt_0.5 are precipitated by heating a rheological liquid precursor of cobalt–hydrazine complex and platinum chloride H₂PtCl₆·xH₂O in polymer molecules of poly(vinylpyrrolidone) (PVP) in ethylene glycol. The hydrazine co-reduces nascent atoms from the Co²⁺ and Pt⁴⁺ that recombine and grow as Co_0.5Pt_0.5. The PVP molecules cap a growing Co_0.5Pt_0.5 as it achieves a critical size so that it stops growing further in given conditions. X-ray diffraction pattern of a recovered powder reveals a crystalline Co_0.5Pt_0.5 phase (average crystallite size D∼8 nm) of a well-known Fm3m-fcc crystal structure with the lattice parameter a=0.3916 nm (density ρ=14.09 g/cm³). A more ordered L1₀ phase (ρ=15.91 g/cm³) transforms (D≥25 nm) upon annealing the powder at temperature lesser than 700 °C (in vacuum). At room temperature, the virgin crystallites bear only a small saturation magnetization M_s=5.54 emu/g (D=8 nm) of a soft magnet and it hardly grows on bigger sizes (D≤31 nm) in a canted ferromagnetic structure. A rectangular hysteresis loop is markedly expanded on an optimally annealed L1₀ phase at 800 °C for 60 min, showing a surface modified coercivity H_c=7.781 kOe with remnant ratio M_r/M_s=0.5564, and M_s=39.75 emu/g. Crystallites self-assembled in an acicular shape tailor large H_c from ideal single domains and high magnetocrystalline anisotropy of a hard magnet L1₀ phase.     

Nonselective harvesting of a prey-predator community with infected prey

The present paper deals with the problem of nonselective harvesting in a partly infected prey and predator system in which both the susceptible prey and the predator follow the law of logistic growth and some preys avoid predation by hiding. The dynamical behaviour of the system has been studied in both the local and global sense. The optimal policy of exploitation has been derived by using Pontraygin’s maximal principle. Numerical analysis and computer simulation of the results have been performed to investigate the global properties of the system.