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

Yishai Albeck, Katharine G. Lunny, Yanice Benitez, Ashley J. Shin, Daniel Strasser*, Robert E. Continetti

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The photoexcitation of cold oxyallyl anions was studied below the adiabatic detachment threshold at a photon energy of 1.60 eV. Photodetachment was observed through two product channels, delayed electron emission from a long-lived anionic state and dissociative photodetachment via absorption of a second photon. The former produced stable neutral C 3 H 4 O, while the latter resulted in the concerted elimination of CO+C 2 H 4 products. The neutral oxyallyl singlet state has a barrier-free route to cyclopropanone as well as zwitterionic character with a large charge separation and dipole moment. The role of long-lived dipole-bound resonances built on the singlet state below the detachment threshold is discussed. These results provide one of the first observations of delayed photoemission in a small cold molecular radical anion, a consequence of the complex electronic structure of the neutral diradical, and provide an example of resonance-mediated control of the photodissociation processes.

Original languageAmerican English
Pages (from-to)5312-5315
Number of pages4
JournalAngewandte Chemie - International Edition
Volume58
Issue number16
DOIs
StatePublished - 8 Apr 2019

Bibliographical note

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • anions
  • delayed photoemission
  • dipole-bound states
  • molecular dynamics
  • photoelectron spectroscopy

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