American Chemical Society
jp5b09151_si_001.xls (269.5 kB)

Collision Cross Sections for O + Ar+ Collisions in the Energy Range 0.03–500 eV

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posted on 2016-01-07, 00:00 authored by A. A. Sycheva, G. G. Balint-Kurti, A. P. Palov
The interatomic potentials of the a2Π and b2Π states of the OAr+ molecule are calculated using the relativistic complete-active space Hartree–Fock method followed by a multireference configuration interaction calculation with an aug-cc-pwCVNZ-DK basis sets where N is 4 and 5. The calculations were followed by an extrapolation to the complete basis set limit. An avoided crossing between the two potential energy curves is found at an internuclear separation of 5.75 bohr (3.04 Å). As the transition probability between the curves is negligible in the relative collision energy range 0.03–500 eV of interest here, collisions on the lower adiabatic a2Π potential may be treated without reference to the upper state. For low energies and orbital angular momentum quantum numbers, the one-dimensional radial Schrödinger equation is solved numerically using a Numerov algorithm method to determine the phase shift. The semiclassical JWKB approximation was employed for relative energies greater than 5 eV and orbital angular quantum numbers higher than 500. Differential, integral, transport (diffusion), and viscosity cross sections for elastic collisions of oxygen atoms with argon ions are calculated for the first time for the range of relative collision energies studied. The calculated cross sections are expected to be of utility in the fields of nanotechnology and arc welding. The combination of an Ar+(2P) ion and a O­(3P) atom gives rise to a total of 12 different molecular electronic states that are all coupled by spin–orbit interactions. Potential energy curves for all 12 states are computed at the complete active space self-consistent field (CASSCF) level and scattering calculations performed. The results are compared with those obtained using just the lowest potential energy curve.