The exothermic seven atom reaction F + HOCH3 → HF + OCH3 reaction was studied by photoelectron-photofragment coincidence (PPC) spectroscopy carried out on the F–(HOCH3) anion at 4.80 eV. This serves as a natural extension of recent work done in our lab on the dissociative photodetachment (DPD) of the F–H2O anion.[1] Here we observe dissociative photodetachment to both the lower energy products (HF + OCH3 + e–) and higher lying reactants (F + HOCH3 + e–). The HF + OH products dominate the spectrum, with a vibrational population inversion in the HF fragment. Like in the simpler F + H2O → HF + OH system, the OCH3 fragment behaves as a spectator to the reaction, produced predominantly without vibrational excitation. Photodetachment at 4.80 eV accesses the long-lived product channel van der Waals complex (FH—OCH3) and the shallow reactant channel van der Waals complex (F—HOCH3). Near threshold photodetachment at 3.20 eV allows for a more detailed examination of this product channel complex, resulting in a clear vibrational progression consistent with the FH–O stretching mode. These observations will be discussed in the context of recent neutral potential surfaces.[2] This work was funded by the United States Department of Energy, Basic Energy Sciences under grant number DE-FG03-98ER14879. [1] R. Otto, J. Ma, A.W. Ray, J.S. Daluz, J. Li, H. Guo, R.E. Continetti, Science 343 (2014) 396. [2] H. Feng, K.R. Randall, H.F. Schaefer, The Journal of Physical Chemistry A 119 (2015) 1636.

Dynamics of the F + HOCH3 → HF + OCH3 reaction

251st National Meeting (2016)

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