Isomer-specific, high-resolution photoelectron spectra of α- and β-furanyl obtained via slow electron velocity-map imaging of cryogenically cooled anions are reported. The spectra yield electron affinities of 1.8546(4) and 1.6566(4) eV for the α- and β-furanyl neutral radicals, respectively. New vibronic structure is resolved and assigned based on density functional theory and Franck-Condon simulations, providing several vibrational frequencies for the ground electronic state of both neutral isomers. Subtle differences in orbital hybridization resulting from varying proximity of the deprotonated carbon to the heteroatom are inferred from photoelectron angular distributions, and the Cβ[sbnd]H bond dissociation energy is estimated from a combination of experimental and theoretical results to be 119.9(2) kcal mol−1.
All Science Journal Classification (ASJC) codes
- Atomic and Molecular Physics, and Optics
- Physical and Theoretical Chemistry
- Aromatic heterocycle
- Photoelectron spectroscopy
- Velocity-map imaging