Quantum dynamics studies of the Na(3S) + HF and Na(3S/3P) + DF reactions: The effects of the initial rotational excitation and the isotopic substitution

• Published in: Chemical physics letters 2019-09, Vol.730, p.378-383
• Main Authors: Yan, Wei, Tan, Rui Shan, Lin, Shi Ying
• Format: Article
• Language: English
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2019.06.035

[Display omitted] •We present accurate quantum wave packet studies for the Na(3S, 3P) + XF (X = H,D) reactions for the first time, employing the best available potential energy surface (PES) and considering the non-adiabatic effects arising from the inter-state coupling between the 3S and 3P states.•The study reveals significant isotopic effects from which we derived that the dissociation of the exciplex, the intermediate complex formed in the Na(3P) + DF reaction, is statistical to a considerable degree.•The results for the effects of the initial rotational state excitations on the Na(3S) + HF reaction are in qualitative agreement with the experiment calling for further refinement of the PES as well as the experimental investigations. Accurate quantum dynamics calculations have been carried out for the Na(3S) + DF(ν = 1–4, j = 0) → NaF + D, Na(3P) + DF(ν = 0, j = 0) → NaF + D/Na(3S) + DF and Na(3S) + HF(ν = 2–4, j = 2,4,6,9) → NaF + H reactions. The isotopic substitution decreases the reactivity remarkably in both Na(3S) + HF and Na(3P) + HF. The calculation also shows that effects of the initial rotational excitations for Na(3S) + HF are different between the process with threshold (v = 2) and those without thresholds (v = 3–4).