Resonance‐Mediated Below‐Threshold Delayed Photoemission and Non‐Franck–Condon Photodissociation of Cold Oxyallyl Anions

Abstract

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Recapture of the Nonvalence Excess Electron into the Excited Valence Orbital Leads to the Chemical Bond Cleavage in the Anion

“…The dipole-bound state (DBS), − in which the electron is loosely bound to the radical moiety by a monopole–dipole long-range force, has been regarded as the nonvalence state of the anion species. − The electronically excited DBS is especially ubiquitous and has been known to play an important role as a “doorway state” in the formation of the interstellar anion species − or electron-mediated biological information transfer. − The DBS is metastable though, especially when its rovibrational states are above the detachment threshold, as it suffers the autodetachments via Feshbach resonances. , Although there have been a number of theoretical predictions , and experimental estimations − regarding autodetachment rates, the first direct measurement of the state-specific autodetachment rates of the DBS (or quadruple-bound state) was reported only quite recently by our group. On the other hand, the relaxation dynamics of the DBS at the (state-specific) molecular level has been little studied to date, although there have been a few femtosecond time-resolved studies identifying the dynamic role of the DBS in the relaxation processes in some interesting biological systems. ,,, As the excess electron in the DBS is nonvalent in nature, understanding of the relaxation mechanism into the valence states is not straightforward.…”