Communication: Probing the entrance channels of the X + CH4 → HX + CH3 (X = F, Cl, Br, I) reactions via photodetachment of X--CH4

Min Cheng, Yuan Feng, Yikui Du, Qihe Zhu, Weijun Zheng, Gábor Czakó, Joel M. Bowman

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The entrance channel potentials of the prototypical polyatomic reaction family X + CH4 → HX + CH3 (X = F, Cl, Br, I) are investigated using anion photoelectron spectroscopy and high-level ab initio electronic structure computations. The pre-reactive van der Waals (vdW) wells of these reactions are probed for X = Cl, Br, I by photodetachment spectra of the corresponding X--CH4 anion complex. For F-CH4, a spin-orbit splitting (∼1310 cm-1) much larger than that of the F atom (404 cm-1) was observed, in good agreement with theory. This showed that in the case of the F-CH4 system the vertical transition from the anion ground state to the neutral potentials accesses a region between the vdW valley and transition state of the early-barrier F + CH4 reaction. The doublet splittings observed in the other halogen complexes are close to the isolated atomic spin-orbit splittings, also in agreement with theory.

Original languageEnglish
Article number191102
JournalJournal of Chemical Physics
Volume134
Issue number19
DOIs
Publication statusPublished - May 21 2011

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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