2017/05/29 by Roman Čurík, Chris H. Greene · 1 citation
Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Atomic and Molecular Physics #Dissociation (chemistry) #Dissociative recombination #Electron #Excitation #Excited state #Inelastic collision #Laser-Matter Interactions and Applications #Quantum #Rotational–vibrational spectroscopy #physics.chem-ph
paper · pdf · doi:10.1063/1.4994921
published as J. Chem. Phys. 147, 054307 (2017)
arxiv created 2017/05/29 · openalex created_date 2017/06/05 · openalex publication_date 2017/08/04 · arxiv updated 2017/10/30 · openalex updated_date 2026/08/06
Inelastic low-energy (0–1 eV) collisions of electrons with HeH+ cations are treated theoretically, with a focus on the rovibrational excitation and dissociative recombination (DR) channels. In an application of ab initio multichannel quantum defect theory, the description of both processes is based on the Born-Oppenheimer quantum defects. The quantum defects were determined using the R-matrix approach in two different frames of reference: the center-of-charge and the center-of-mass frames. The results obtained in the two reference systems, after implementing the Fano-Jungen style rovibrational frame-transformation technique, show differences in the rate of convergence for these two different frames of reference. We find good agreement with the available theoretically predicted rotationally inelastic thermal rate coefficients. Our computed DR rate also agrees well with the available experimental results. Moreover, several computational experiments shed light on the role of rotational and vibrational excitations in the indirect DR mechanism that governs the low energy HeH+ dissociation process. While the rotational excitation is several orders of magnitude more probable process at the studied collision energies, the closed-channel resonances described by the high-n, rotationally excited neutral molecules of HeH contribute very little to the dissociation probability. But the situation is very different for resonances defined by the high-n, vibrationally excited HeH molecules, which are found to dissociate with approximately 90% probability.