Hyperfine-Resolved Rotational Spectroscopy of Phenyl Radical

J Phys Chem Lett. 2023 Jun 15;14(23):5370-5376. doi: 10.1021/acs.jpclett.3c01243. Epub 2023 Jun 6.

Abstract

We present an analysis of the hyperfine-resolved rotational spectrum of gas-phase phenyl radical, c-C6H5, between 9 and 35 GHz. The isotropic and anisotropic hyperfine parameters of all five protons and the electronic spin-rotation fine structure parameters are accurately determined from this study, which allow detailed insight into the distribution and interactions of the unpaired electron in this prototypical σ-radical. The implications for laboratory and astronomical investigations of phenyl that are reliant on a precise centimeter-wave catalog are discussed, as are the prospects for detecting and assigning the hyperfine-resolved rotational spectra of other large, weakly polar hydrocarbon chain and ring radicals.