Continuous absorption and emission of light by the heteronuclear rare gas (ArXe)+ and (KrXe)+ ions

• Published in: The Journal of Chemical Physics
• Main Authors: Narits, A. A., Kislov, K. S., Lebedev, V. S.
• Other Authors: Russian Science Foundation
• Format: Article in Journal/Newspaper
• Language: English
• Published: AIP Publishing 2022
• Subjects: Physical and Theoretical Chemistry; General Physics and Astronomy; Orca
• Online Access: http://dx.doi.org/10.1063/5.0118068; https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0118068/16555169/204307_1_online.pdf

Studies of radiative transitions between ground and charge transfer excited terms of heteronuclear rare-gas (ArXe)+ and (KrXe)+ ions with small and moderate dissociation energies (D0ArXe+=179 and D0KrXe+=389 meV) are reported. Potential energy curves and dipole transition matrix elements are evaluated using ab initio calculations based on the CASSCF method followed by the NEVPT2 treatment and perturbative description of relativistic effects as implemented in the ORCA suite. We develop an efficient approach for the calculations of Boltzmann-averaged cross sections, rate constants, and absorption and emission coefficients associated with the integral contributions of bound–bound and bound–free transitions from a manifold of rovibrational states of the (RgXe)+ ion. A similar approach is used for the description of the free–free and free–bound transitions between different electronic terms of a quasimolecular (RgXe)+ ion temporarily formed during a collision of Ar or Kr atoms with Xe+ ions. Our method is based on the quantal version of the theory of non-adiabatic transitions in molecular and quasimolecular systems combined with the approximation of a quasicontinuum for rovibrational energy levels. This allowed us to obtain a semianalytic expression for the integral absorption properties particularly relevant at elevated temperatures. We perform a comprehensive analysis of the identified radiative processes in local thermodynamic equilibrium plasmas of rare gas Rg/Xe mixtures containing both atomic, Xe+, and molecular, RgXe+, ions and determine their role in the formation of the absorption and emission spectra in a wide range of wavelengths and gas temperatures. The results obtained are in good agreement with the available experimental data.