Evidence for electron spin-torsion coupling in the rotational spectrum of the CH$_3$CO radical

Abstract

Open-shell non-rigid molecular systems exhibiting an internal rotation are likely candidates for a coupling between the spin angular momentum of the unpaired electron and the torsional motion. This electron spin-torsion coupling lacked both an experimental validation and a theoretical modeling. Here, the first experimental observation of the electron spin-torsion coupling is reported analyzing the pure rotational spectrum at millimeter wavelengths of the CH$_3$CO radical, a $^2\Sigma$ open-shell molecule displaying an internal rotation of its methyl group. To account for this coupling, a specific Hamiltonian incorporating the rotational, torsional, and electronic degrees of freedom is developed and allows us to reproduce the experimental spectrum. The present demonstration of the electron spin-torsion coupling will undoubtedly be key to future investigations of large open-shell molecules exhibiting a complex internal dynamics.