title: Communication: probing the entrance channels of the X+CH4→HX+CH3 (X = F, Cl, Br, I) reactions via photodetachment of X(-)-CH4.
abstract: The entrance channel potentials of the prototypical polyatomic reaction family X + CH(4) → HX + CH(3) (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(-)-CH(4) anion complex. For F-CH(4), 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-CH(4) 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 + CH(4) reaction. The doublet splittings observed in the other halogen complexes are close to the isolated atomic spin-orbit splittings, also in agreement with theory.
authors: National Laboratory of Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors: Min
authors: M
authors: Cheng
authors: Yuan
authors: Y
authors: Feng
authors: Yikui
authors: Y
authors: Du
authors: Qihe
authors: Q
authors: Zhu
authors: Weijun
authors: W
authors: Zheng
authors: Gábor
authors: G
authors: Czakó
authors: Joel M
authors: JM
authors: Bowman