Probing the activated complex of the F + NH<sub>3</sub> reaction via a dipole-bound state.

Zhang, Rui; Yan, Shuaiting; Song, Hongwei; Guo, Hua; Ning, Chuangang · Nat Commun · 2024

basic_science · Level V

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Abstract

Experimental characterization of the transition state poses a significant challenge due to its fleeting nature. Negative ion photodetachment offers a unique tool for probing transition states and their vicinity. However, this approach is usually limited to Franck-Condon regions. For example, high-lying Feshbach resonances with an excited HF stretching mode (v<sub>HF</sub> = 2-4) were recently identified in the transition-state region of the F + NH<sub>3</sub> → HF + NH<sub>2</sub> reaction through photo-detaching FNH<sub>3</sub><sup>-</sup> anions, but the direct photodetachment failed to observe the lower-lying v<sub>HF</sub> = 0,1 resonances and bound states due apparently to negligible Franck-Condon factors. Indeed, these weak transitions can be resonantly enhanced via a dipole-bound state (DBS) formed between an electron and the polar FNH<sub>3</sub> species. In this study, we unveil a series of Feshbach resonances and bound states along the F + NH<sub>3</sub> reaction path via a DBS by combining high-resolution photoelectron spectroscopy with high-level quantum dynamical computations. This study presents an approach for probing the activated complex in a reaction by negative ion photodetachment through a DBS.