Spectroscopy of Na⁺·Rg and transport coefficients of Na⁺ in Rg (Rg=He-Rn)

High-level ab initio calculations are used to obtain accurate potential energy curves for Na+·Kr, Na+·Xe, and Na+·Rn. These data are used to calculate spectroscopic parameters for these three species, and the data for the whole Na+·Rg series (Rg=He-Rn) are compared. Potentials for the whole series are then used to calculate both mobilities and diffusion coefficients for Na+ moving through a bath of each of the six rare gases, under conditions that match previous experimental determinations. Different available potentials and experimental data are then statistically compared. It is concluded that the present potentials are very accurate. The potential and other data for Na+·Rn appear to be the first such reported

Spectroscopy of Na+⋅Rg and transport coefficients of Na+ in Rg(Rg=He–Rn)

High-level ab initio calculations are used to obtain accurate potential energy curves for Na+·Kr, Na+·Xe, and Na+·Rn. These data are used to calculate spectroscopic parameters for these three species, and the data for the whole Na+·Rg series (Rg=He-Rn) are compared. Potentials for the whole series are then used to calculate both mobilities and diffusion coefficients for Na+ moving through a bath of each of the six rare gases, under conditions that match previous experimental determinations. Different available potentials and experimental data are then statistically compared. It is concluded that the present potentials are very accurate. The potential and other data for Na+·Rn appear to be the first such reported

Calculations on the unstable CO-(X-2II) anion

It is demonstrated that CO-(X(2)Pi) lies above CO(X(1)Sigma (+)) and hence is unstable with respect to autodetachment. This is in disagreement with an oft-cited experimental result, which concluded that CO has an electron affinity of +1.4 eV, but in agreement with electron scattering results. It might be concluded that the RCCSD(T) approach with aug-cc-pVQZ and aug-cc-pV5Z basis sets gives reliable electron affinities based upon comparison with identical calculations on N-2; however, analysis of the electronic wave function indicates that this may be fortuitous. On the other hand, CASSCF + multireference configuration interaction (MRCI) calculations on CO- seem to indicate a viable way forward, and spectroscopic constants are derived

Spectroscopy of Na⁺·Rg and transport coefficients of Na⁺ in Rg (Rg=He-Rn)

High-level ab initio calculations are used to obtain accurate potential energy curves for Na+·Kr, Na+·Xe, and Na+·Rn. These data are used to calculate spectroscopic parameters for these three species, and the data for the whole Na+·Rg series (Rg=He-Rn) are compared. Potentials for the whole series are then used to calculate both mobilities and diffusion coefficients for Na+ moving through a bath of each of the six rare gases, under conditions that match previous experimental determinations. Different available potentials and experimental data are then statistically compared. It is concluded that the present potentials are very accurate. The potential and other data for Na+·Rn appear to be the first such reported

Spectroscopy of Li+·Rg and Li+–Rg transport coefficients (Rg = He–Rn)

High-quality [CCSD(T), large basis sets] ab initio potential energy curves are calculated for the series of Li+·Rg species. These curves are employed to calculate spectroscopic parameters for these species, and are used to calculate transport properties for Li+ moving through a bath of the relevant inert gas. The transport results obtained are statistically compared to previous ones. The present potentials appear to be the best available for Li+·Ar, Li+·Kr and Li+·Xe and they rival the best ones for Li+·He and Li+·Ne. In the case of the Li+·Rn system, these are the first reported results

An ab initio study of RbO, CsO and FrO (X²? ; A²?) and their cations (X³?? ; A³?)

High-level [RCCSD(T)] ab initio calculations are employed to generate sets of data from which spectroscopic constants for the title species could be derived. For O, the standard aug-cc-pV5Z (no h) basis set was employed, while for the metal atoms an effective core potential combined with a large, flexible valence basis set was used. Calculated ionization energies for the metal atoms, and the calculated electron affinity of O suggest that both types of basis set are performing well. The calculated constants are, in general, in good agreement with previous experimental and theoretical studies, where available. A simple ionic model is employed to obtain ionization energies, and the resulting values are compared to those calculated at the RCCSD(T) level, as well as previous experimental values. Finally, dissociation energies of the title species are also calculated