Structural Characterization of Phenoxy Radical with Mass-Correlated Broadband Microwave Spectroscopy.

Abstract

A combination of broadband microwave spectroscopy and VUV photoionization time-of-flight mass spectra has been used to record rotational spectra of the prototypical phenoxy radical, its per-deuterated isotopomers, and the full set of singly 13C-substituted analogues. Rotational parameters associated with the fits to the full set of isotopomers produce a highly accurate r0 structure for the phenoxy radical. High-level ab initio calculations accurately reproduce the rotational constants and spin-rotation parameters. The structure of the phenoxy radical is distinctly quinoidal, with delocalization of the unpaired electron spin density on the oxygen and phenyl ring. The fitted Fermi contact terms for the 13C atoms reflect a weighting of resonance structures that is 27% on the O atom, 21.5% on each of the two ortho C's, and 30% on the para C, providing a quantitative measure of its sites for subsequent reactions that will control its abundances in combustion and atmospheric environments.