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Issue 2, 2014
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On the signal depletion induced by stretching excitation of methane in the reaction with the F atom

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Abstract

Exciting a stretching mode of a chemical bond should help its breaking during a chemical reaction, according to conventional wisdom. In several recent studies of the reactions of stretch-excited methane (and isotopologues) with the F atom, counterintuitively, we found that the induced reactant vibrations instead inhibit the bond rupture and slow down the overall reaction rate. This intriguing observation has been qualitatively ascribed to the vibrationally induced steric effects of the reaction in previous reports. However, quantitative determination of the reactivity suppression in terms of reaction cross sections remains lacking. In this report, we scrutinize the physical meaning of this (product) signal depletion phenomenon and fill the gap. Through a systematic investigation we further elucidate the additional reaction dynamics information that can be retrieved from the depletion measurements. The resultant rotationally state-selected reaction cross sections for both the vibrational ground and excited states are presented, and the stereodynamical implications are delineated.

Graphical abstract: On the signal depletion induced by stretching excitation of methane in the reaction with the F atom

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Publication details

The article was received on 19 Jul 2013, accepted on 27 Aug 2013 and first published on 18 Sep 2013


Article type: Paper
DOI: 10.1039/C3CP53036A
Phys. Chem. Chem. Phys., 2014,16, 444-452

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    On the signal depletion induced by stretching excitation of methane in the reaction with the F atom

    Y. Cheng, H. Pan, F. Wang and K. Liu, Phys. Chem. Chem. Phys., 2014, 16, 444
    DOI: 10.1039/C3CP53036A

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