On Molecular Origin of Mass-Independent Fractionation of Oxygen Isotopes in the Ozone Forming Recombination Reaction

Theoretical treatment of ozone forming reaction is developed within the framework of mixed quantum/classical dynamics. Formation and stabilization steps of the energy transfer mechanism are both studied, which allows simultaneous capture of the delta zero-point energy effect and η-effect and identification of the molecular level origin of mass-independent isotope fractionation. The central role belongs to scattering resonances; dependence of their lifetimes on rotational excitation, asymmetry; and connection of their vibrational wave functions to two different reaction channels. Calculations, performed within the dimensionally reduced model of ozone, are in semiquantitative agreement with experiment

On Stabilization of Scattering Resonances in Recombination Reaction that Forms Ozone

Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results indicate no difference in cross sections for stabilization of scattering resonances in symmetric and asymmetric isotopomers. As practical results, the general and simple analytic models for stabilization and dissociation cross sections are presented, which can be applied to resonances in any ozone molecule, symmetric or asymmetric, singly or doubly substituted. Present calculations show some isotope effect that looks similar to the experimentally observed η-effect, and the origin of this phenomenon is in the rates of formation/decay of scattering resonances, determined by their widths, that are somewhat larger in asymmetric isotopomers than in their symmetric analogues. However, the approximate two-dimensional model used here is insufficient for consistent and reliable description of all features of the isotopic effect in ozone. Calculations using an accurate 3D model are still needed

Ro-vibrational Quenching of CO (\u3cem\u3ev\u3c/em\u3e = 1) by He Impact in a Broad Range of Temperatures: A Benchmark Study Using Mixed Quantum/Classical Inelastic Scattering Theory

The mixed quantum/classical approach is applied to the problem of ro-vibrational energy transfer in the inelastic collisions of CO(v = 1) with He atom, in order to predict the quenching rate coefficient in a broad range of temperatures 5 \u3c T \u3c 2500 K. Scattering calculations are done in two different ways: direct calculations of quenching cross sections and, alternatively, calculations of the excitation cross sections plus microscopic reversibility. In addition, a symmetrized average-velocity method of Billing is tried. Combination of these methods allows reproducing experiment in a broad range of temperatures. Excellent agreement with experiment is obtained at 400 \u3c T \u3c 2500 K (within 10%), good agreement in the range 100 \u3c T \u3c 400 K (within 25%), and semi-quantitative agreement at 40 \u3c T \u3c 100 K(within a factor of 2). This study provides a stringent test of the mixed quantum/classical theory, because the vibrational quantum in CO molecule is rather large and the quencher is very light (He atom). For heavier quenchers and closer to dissociation limit of the molecule, the mixed quantum/classical theory is expected to work even better

Rotational Quenching of H\u3csub\u3e2\u3c/sub\u3eO by He: Mixed Quantum/Classical Theory and Comparison with Quantum Results

The mixed quantum/classical theory (MQCT) formulated in the space-fixed reference frame is used to compute quenching cross sections of several rotationally excited states of water molecule by impact of He atom in a broad range of collision energies, and is tested against the full-quantum calculations on the same potential energy surface. In current implementation of MQCT method, there are two major sources of errors: one affects results at energies below 10 cm−1, while the other shows up at energies above 500 cm−1. Namely, when the collision energy E is below the state-to-state transition energy ΔE the MQCT method becomes less accurate due to its intrinsic classical approximation, although employment of the average-velocity principle (scaling of collision energy in order to satisfy microscopic reversibility) helps dramatically. At higher energies, MQCT is expected to be accurate but in current implementation, in order to make calculations computationally affordable, we had to cut off the basis set size. This can be avoided by using a more efficient body-fixed formulation of MQCT. Overall, the errors of MQCT method are within 20% of the full-quantum results almost everywhere through four-orders-of-magnitude range of collision energies, except near resonances, where the errors are somewhat larger

Backward scattering of low-energy antiprotons by highly charged and neutral uranium: Coulomb glory

Collisions of antiprotons with He-, Ne-, Ni-like, bare, and neutral uranium are studied theoretically for scattering angles close to 180$^{\circ}$ and antiproton energies with the interval 100 eV -- 10 keV. We investigate the Coulomb glory effect which is caused by a screening of the Coulomb potential of the nucleus and results in a prominent maximum of the differential cross section in the backward direction at some energies of the incident particle. We found that for larger numbers of electrons in the ion the effect becomes more pronounced and shifts to higher energies of the antiproton. On the other hand, a maximum of the differential cross section in the backward direction can also be found in the scattering of antiprotons on a bare uranium nucleus. The latter case can be regarded as a manifestation of the screening property of the vacuum-polarization potential in non-relativistic collisions of heavy particles.Comment: 14 pages, 5 figure

On the bound state of the antiproton-deuterium-tritium ion

The properties of the weakly-bound $S(L = 0)-$state in the $\bar{p}dt$ ion are investigated with the use of the results of highly accurate computations. The hyperfine structure splitting of this ion is investigated. We also evaluate the life-time of the $\bar{p}dt$ ion against the nuclear $(d,t)-$fusion and discuss a possibility to evaluate the corresponding annihilation rate(s)

The HITRAN2012 molecular spectroscopic database

This paper describes the status of the 2012 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2008 and its updates during the intervening years. The HITRAN molecular absorption compilation is comprised of six major components structured into folders that are freely accessible on the internet. These folders consist of the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, ultraviolet spectroscopic parameters, aerosol indices of refraction, ision-induced absorption data, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, and validity. Molecules and isotopologues have been added that address the issues of atmospheres beyond the Earth. Also discussed is a new initiative that casts HITRAN into a relational database format that offers many advantages over the long-standing sequential text-based structure that has existed since the initial release of HITRAN in the early 1970s. (C) 2013 Elsevier Ltd. All rights reserved

Cluster virial expansion for the equation of state of partially ionized hydrogen plasma

We study the contribution of electron-atom interaction to the equation of state for partially ionized hydrogen plasma using the cluster-virial expansion. For the first time, we use the Beth-Uhlenbeck approach to calculate the second virial coefficient for the electron-atom (bound cluster) pair from the corresponding scattering phase-shifts and binding energies. Experimental scattering cross-sections as well as phase-shifts calculated on the basis of different pseudopotential models are used as an input for the Beth-Uhlenbeck formula. By including Pauli blocking and screening in the phase-shift calculation, we generalize the cluster-virial expansion in order to cover also near solid density plasmas. We present results for the electron-atom contribution to the virial expansion and the corresponding equation of state, i.e. pressure, composition, and chemical potential as a function of density and temperature. These results are compared with semi-empirical approaches to the thermodynamics of partially ionized plasmas. Avoiding any ill-founded input quantities, the Beth-Uhlenbeck second virial coefficient for the electron-atom interaction represents a benchmark for other, semi-empirical approaches.Comment: 16 pages, 10 figures, and 5 tables, resubmitted to PR

Algebraic Model for scattering in three-s-cluster systems. I. Theoretical Background

A framework to calculate two-particle matrix elements for fully antisymmetrized three-cluster configurations is presented. The theory is developed for a scattering situation described in terms of the Algebraic Model. This means that the nuclear many-particle state and its asymptotic behaviour are expanded in terms of oscillator states of the intra-cluster coordinates. The Generating Function technique is used to optimize the calculation of matrix elements. In order to derive the dynamical equations, a multichannel version of the Algebraic Model is presented.Comment: 20 pages, 1 postscript figure, submitted to Phys. Rev.

Scattering states of coupled valence-band holes in point defect potential derived from variable phase theory

In this article we present a method to compute the scattering states of holes in spherical bands in the strong spin-orbit coupling regime. More precisely, we calculate scattering phase shifts and amplitudes of holes induced by defects in a semiconductor crystal. We follow a previous work done on this topic by Ralph [H. I. Ralph, Philips Res. Rept. 32 160 (1977)] to account for the p-wave nature and the coupling of valence band states. We extend Ralph's analysis to incorporate finite-range potentials in the scattering problem. We find that the variable phase method provides a very convenient framework for our purposes and show in detail how scattering amplitudes and phase shifts are obtained. The Green's matrix of the Schroedinger equation, the Lippmann-Schwinger equation and the Born approximation are also discussed. Examples are provided to illustrate our calculations with Yukawa type potentials.Comment: 16 pages and 9 figure