The Determination of Rate Constants from Known Linear Combinations of Concentrations in a Chemical Reaction

The determination of rate constants from known linear combinationsof concentrations in a chemical reaction is studied. Continuousdependence of the rate constants upon the data is demonstrated.A nonlinear least-squares method of approximation of the rateconstants is formulated and utilized in some numerical studies.     

Theoretical prediction of a linear isomer for NeBr2(X1Γg + an ab initio approach

A supermolecular approach is used to predict the stationary structures of the NeBr₂(X¹Γ_g ⁺) van der Waals cluster. The intermolecular potential is calculated using the single and double excitation coupled-cluster method with non-iterative perturbation treatment of triple excitations [CCSD(T)]. Relativistic effects are included for the Br atoms using effective core potentials (ECPs) and their efficiency is tested for Br₂ and NeBr₂ molecules. Our results for NeBr₂ show minima for both linear and T-shaped configurations, in accord with previous ab initio calculations for rare gas-Br₂ species. The dependence of the interaction potential, as a function of the Br-Br bond, is also presented. Finally, vibrational analysis is carried out to examine the stability of the two isomers including zero-point vibrational energy effects.     

An accurate,global, ab initio potential energy surface for the H+ 3 molecule

A new global, ground-state, Born-Oppenheimer surface is presented for the H⁺ ₃ system. The energy switching approach has been used to combine different functional forms for three different regimes: a spectroscopic expansion at low energy, a Sorbie-Murrell function at high energy and known long-range terms combined with accurate diatomic potentials at large separations. At low energies we have used the ultra high accuracy ab initio data of Cencek et al. (1998, J. chem. Phys., 108, 2831). At intermediate energy we have calculated 134 new ab initio energies using a high accuracy, explicitly correlated procedure. The ab initio data of Schinke et al. (1980, J. chem. Phys., 72, 3909) has been used to constrain the high energy region. Two fits are presented which differ somewhat in their behaviour at energies over 45 000 cm^?1 above the H⁺ ₃ minimum. Below this energy, the fits reproduce each set of ab initio data close to their intrinsic accuracy. The ground state surface should provide a suitable starting point for renewed studies of the near-threshold photodissociation spectrum originally reported by Carrington et al. (1982, Molec. Phys., 45, 753).     

Measurement of 232Th(n, γ) and 232Th({n}, {2n}) cross-sections at neutron energies of 13.5, 15.5 and 17.28?MeV using neutron activation techniques

The ²³²Th(n, ??) reaction cross-section at average neutron energies of 13.5, 15.5 and 17.28?MeV from the ⁷Li(p, n) reaction has been determined for the first time using activation and off-line ??-ray spectrometric technique. The ²³²Th(n, 2n) cross-section at 17.28?MeV neutron energy has also been determined using the same technique. The experimentally determined ²³²Th(n, ??) and ²³²Th(n, 2n) reaction cross-sections from the present work were compared with the evaluated data of ENDF/BVII and JENDL-4.0 and were found to be in good agreement. The present data, along with literature data in a wide range of neutron energies, were interpreted in terms of competition between ²³²Th(n, ??), (n, f), (n, nf) and (n, xn) reaction channels. The ²³²Th(n, ??) and ²³²Th(n, 2n) reaction cross-sections were also calculated theoretically using the TALYS 1.2 computer code and were found to be in good agreement with the experimental data from the present work but were slightly higher than the literature data at lower neutron energies.