Communication: Probing the entrance channels of the X + CH{sub 4}{yields} HX + CH{sub 3} (X = F, Cl, Br, I) reactions via photodetachment of X{sup -}-CH{sub 4}

Journal Article · Sat May 21 00:00:00 EDT 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3591179· OSTI ID:21560242

Min, Cheng; Yuan, Feng; Yikui, Du; Qihe, Zhu; Weijun, Zheng ^[1]; Czako, Gabor; Bowman, Joel M ^[2]

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1. National Laboratory of Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
2. Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)

The entrance channel potentials of the prototypical polyatomic reaction family X + CH{sub 4}{yields} HX + CH{sub 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{sup -}-CH{sub 4} anion complex. For F-CH{sub 4}, a spin-orbit splitting ({approx}1310 cm{sup -1}) much larger than that of the F atom (404 cm{sup -1}) was observed, in good agreement with theory. This showed that in the case of the F-CH{sub 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{sub 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.

• OSTI ID: 21560242
• Journal Information: Journal of Chemical Physics, Vol. 134, Issue 19; Other Information: DOI: 10.1063/1.3591179; (c) 2011 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANIONS
ATOMS
BROMINE
CALCULATION METHODS
CHLORINE
COMMUNICATIONS
COMPLEXES
ELECTRON DETACHMENT
ELECTRONIC STRUCTURE
FLUORINE
GROUND STATES
IODINE
METHANE
PHOTOELECTRON SPECTROSCOPY
POTENTIALS
SPECTRA
SPIN
VAN DER WAALS FORCES
ALKANES
ANGULAR MOMENTUM
CHARGED PARTICLES
ELECTRON SPECTROSCOPY
ELEMENTS
ENERGY LEVELS
HALOGENS
HYDROCARBONS
IONS
NONMETALS
ORGANIC COMPOUNDS
PARTICLE PROPERTIES
SPECTROSCOPY