TY - JOUR
T1 - Resonances in the entrance channel of the elementary chemical reaction of fluorine and methane
AU - Westermann, Till
AU - Kim, Jongjin B.
AU - Weichman, Marissa L.
AU - Hock, Christian
AU - Yacovitch, Tara I.
AU - Palma, Juliana
AU - Neumark, Daniel M.
AU - Manthe, Uwe
PY - 2014/1/20
Y1 - 2014/1/20
N2 - Extending the fully quantum-state-resolved description of elementary chemical reactions beyond three or four atom systems is a crucial issue in fundamental chemical research. Reactions of methane with F, Cl, H or O are key examples that have been studied prominently. In particular, reactive resonances and nonintuitive mode-selective chemistry have been reported in experimental studies for the F+CH4→HF+CH3 reaction. By investigating this reaction using transition-state spectroscopy, this joint theoretical and experimental study provides a clear picture of resonances in the F+CH4 system. This picture is deduced from high-resolution slow electron velocity-map imaging (SEVI) spectra and accurate full-dimensional (12D) quantum dynamics simulations in the picosecond regime. Chemical reactivity: Experimental and theoretical data consistently demonstrate the existence of resonances in the entrance channel of the F+CH4→HF+CH 3 reaction shown by transition-state spectroscopy (see picture; ΔSO=atomic spin-orbit splitting). Based on full-dimensional quantum dynamics simulations, a clear picture is drawn explaining the resonances.
AB - Extending the fully quantum-state-resolved description of elementary chemical reactions beyond three or four atom systems is a crucial issue in fundamental chemical research. Reactions of methane with F, Cl, H or O are key examples that have been studied prominently. In particular, reactive resonances and nonintuitive mode-selective chemistry have been reported in experimental studies for the F+CH4→HF+CH3 reaction. By investigating this reaction using transition-state spectroscopy, this joint theoretical and experimental study provides a clear picture of resonances in the F+CH4 system. This picture is deduced from high-resolution slow electron velocity-map imaging (SEVI) spectra and accurate full-dimensional (12D) quantum dynamics simulations in the picosecond regime. Chemical reactivity: Experimental and theoretical data consistently demonstrate the existence of resonances in the entrance channel of the F+CH4→HF+CH 3 reaction shown by transition-state spectroscopy (see picture; ΔSO=atomic spin-orbit splitting). Based on full-dimensional quantum dynamics simulations, a clear picture is drawn explaining the resonances.
KW - ab initio calculations
KW - molecular dynamics
KW - photoelectron spectroscopy
KW - potential-energy surfaces
KW - van der Waals complexes
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U2 - 10.1002/anie.201307822
DO - 10.1002/anie.201307822
M3 - Article
C2 - 24307593
AN - SCOPUS:84893261043
SN - 1433-7851
VL - 53
SP - 1122
EP - 1126
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 4
ER -