Theoretical studies of product polarization and state distributions of the H+HCl reaction

The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.

State-Selective Photodissociation Dynamics of Formaldehyde: Near Threshold Studies of the H+HCO Product Channel

The laser-induced photodissociation of formaldehyde in the wavelength range 309<λ<330nm 309<λ<330nm has been investigated using H (Rydberg) atom photofragment translational spectroscopy. Photolysis wavelengths corresponding to specific rovibronic transitions in the A ˜ A 2 1 ←X ˜ A 1 1 ÃA21←X̃A11 2 1 0 4 3 0 201403 , 2 2 0 4 1 0 202401 , 2 2 0 4 3 0 202403 , 2 3 0 4 1 0 203401 , and 2 1 0 5 1 0 201501 bands of H 2 CO H2CO were studied. The total kinetic energy release spectra so derived can be used to determine partial rotational state population distributions of the HCO cofragment. HCO product state distributions have been derived following the population of various different N K a NKa levels in the A ˜ A 2 1 ÃA21 2 2 4 3 2243 and 2 3 4 1 2341 states. Two distinct spectral signatures are identified, suggesting competition between dissociation pathways involving the X ˜ A 1 1 X̃A11 and the a ˜ A 2 3 ãA23 potential energy surfaces. Most rovibrational states of H 2 CO(A ˜ A 2 1 ) H2CO(ÃA21) investigated in this work produceH+HCO(X ˜ A ′ 2 ) H+HCO(X̃A′2) photofragments with a broad kinetic energy distribution and significant population in high energy rotational states of HCO. Photodissociation via the A ˜ A 2 1 ÃA21 2 2 4 3 2243 1 1,1 11,1 (and 1 1,0 11,0 ) rovibronic states yields predominantly HCO fragments with low internal energy, a signature that these rovibronic levels are perturbed by the a ˜ A 2 3 ãA23 state. The results also suggest the need for further careful measurements of the H+HCO H+HCO quantum yield from H 2 CO H2CO photolysis at energies approaching, and above, the barrier to C–H bond fission on the a ˜ A 2 3 ãA23 potential energy surface.

Recent developments in the quantum dynamical characterization of unimolecular resonances

We give a selective review of quantum mechanical methods for calculating and characterizing resonances in small molecular systems, with an emphasis on recent progress in Chebyshev and Lanczos iterative methods. Two archetypal molecular systems are discussed: isolated resonances in HCO, which exhibit regular mode and state specificity, and overlapping resonances in strongly bound HO2, which exhibit irregular and chaotic behavior. Recent progresses for non-zero total angular momentum J calculations of resonances including parallel computing models are also included and future directions in this field are discussed.

Nonadiabatic photodissociation dynamics

The photodissociation dynamics of the triatomic (or pseudo-triatomic) system in the nonadiabatic multiple electronic states is investigated by employing a time-dependent quantum wavepacket method, while the time propagation of the wave packet is carried out using the split-operator scheme. As a numerical example, the photodissociation dynamics of CH,l in three electronic states (1)Q(1)(A'), (1)Q(1)(A"), and (3)Q(0+) is studied and CH3I is treated as a pseudotriatomic model. The absorption spectra and product vibrational state distributions are calculated and compared with previous theoretical work. (C) 2004 Wiley Periodicals, Inc.

Charge-state distribution and Doppler effect in an expanding photoionized plasma.

The charge state distributions of Fe, Na, and F are determined in a photoionized laboratory plasma using high resolution x-ray spectroscopy. Independent measurements of the density and radiation flux indicate unprecedented values for the ionization parameter ���¾=20 25 erg cm s-1 under near steady-state conditions. Line opacities are well fitted by a curve-of-growth analysis which includes the effects of velocity gradients in a one-dimensional expanding plasma. First comparisons of the measured charge state distributions with x-ray photoionization models show reasonable agreement.

Investigations on Stochastic Storage Systems with Positive Service Time

In this thesis the queueing-inventory models considered are analyzed as continuous time Markov chains in which we use the tools such as matrix analytic methods. We obtain the steady-state distributions of various queueing-inventory models in product form under the assumption that no customer joins the system when the inventory level is zero. This is despite the strong correlation between the number of customers joining the system and the inventory level during lead time. The resulting quasi-birth-anddeath (QBD) processes are solved explicitly by matrix geometric methods

Mining product adopter information from online reviews for improving product recommendation

We present in this article an automated framework that extracts product adopter information from online reviews and incorporates the extracted information into feature-based matrix factorization formore effective product recommendation. In specific, we propose a bootstrapping approach for the extraction of product adopters from review text and categorize them into a number of different demographic categories. The aggregated demographic information of many product adopters can be used to characterize both products and users in the form of distributions over different demographic categories. We further propose a graphbased method to iteratively update user- and product-related distributions more reliably in a heterogeneous user-product graph and incorporate them as features into the matrix factorization approach for product recommendation. Our experimental results on a large dataset crawled from JINGDONG, the largest B2C e-commerce website in China, show that our proposed framework outperforms a number of competitive baselines for product recommendation.

A linear-elastic model of anisotropic tumour growth

This paper examines the effect of anisotropic growth on the evolution of mechanical stresses in a linear-elastic model of a growing, avascular tumour. This represents an important improvement on previous linear-elastic models of tissue growth since it has been shown recently that spatially-varying isotropic growth of linear-elastic tissues does not afford the necessary stress-relaxation for a steady-state stress distribution upon reaching a nutrient-regulated equilibrium size. Time-dependent numerical solutions are developed using a Lax-Wendroff scheme, which show the evolution of the tissue stress distributions over a period of growth until a steady-state is reached. These results are compared with the steady-state solutions predicted by the model equations, and key parameters influencing these steady-state distributions are identified. Recommendations for further extensions and applications of this model are proposed.

Detection of the protein dimers, multiple monomeric states and hydrated forms of Plasmodium falciparum triosephosphate isomerase in the gas phase

Dimeric and monomeric forms of the enzyme triosephosphate isomerase (TIM) from Plasmodium falciparum (Pf) have been detected under conditions of nanoflow by electrospray mass spectrometry. The dimer (M = 55 663 Da) exhibits a narrow charge state distribution with intense peaks limited to values of 18(+) to 21(+), maximal intensity being observed for charge states 19(+) and 20(+). A monomeric species with a charge state distribution ranging from 11(+) to 16(+) is also observed, which may be assigned to folded dissociated subunits. Complete dimer dissociation results under normal electrospray condition. The effects of solution pH and source temperature have been investigated. The observation of four distinct charge state distributions which may be assigned to a dimer, folded monomer, partially folded monomer and unfolded monomer is reported. Circular dichromism and fluorescence studies of Pf TIM at low pH support the retention of substantial secondary and tertiary structures. Satellite peaks in mass spectra corresponding to hydrated species are also observed and isotope shift upon deuteration is demonstrated. The analysis of all available independent crystal structures of Pf TIM and TIMs from other organisms permits identification of structurally conserved water molecules. Hydration observed in the dimer and folded monomeric forms in the gas phase may correspond to these conserved sites.

Studies of multiple ionization in the RF spark and vacuum vibrator arc ion sources

Relative abundance distributions of multiply-charged ionic species have been measured for the RF spark and vacuum vibrator are ion sources, for a number of elements. An attempt has been made to explain the observed charge state distribution on the basis of models for the arc and spark plasma. The difficulties in the way of explaining the observed charge state distributions, using the LTE model with Saha distribution as well as the corona model, are pointed out. The distribution can be explained by a diffusion-dominated plasma model with known or calculated values for ionization cross-sections, the single impact model being suitable for the RF spark and the multiple impact model for the vibrator arc.

Time-dependent analysis of an N2O gasdynamic laser

A simplified two-temperature model is presented for the vibrational energy levels of the N2O and N2 molecules of an N2O-N2-He gasdynamic laser (GDL), and the governing equations for the unsteady flow of the gas mixture in a convergent-divergent contour nozzle are solved using a time-dependent numerical technique. Final steady-state distributions are obtained for vibrational temperatures, population inversion, and the small-signal laser gain along the nozzle. It is demonstrated that, for plenum temperatures lower than 1200 K, an N2O GDL such as the present is more efficient than a CO2 GDL in identical operating conditions