Magnetic properties of free radicals.

The magnetic properties of free radicals provide a powerful tool for their detection and study. Molecules with even numbers of paired electrons are diamagnetic; i.e., they are slightly repelled by a magnet. Free radicals, however, are paramagnetic (attracted by a magnet) because of the spin of the odd electron, the spins of the remaining paired electrons effectively canceling each other. The magnetic property of a substance most commonly studied is its magnetic susceptibility, effectively its behaviour in an inhomogeneous magnetic field, and the extent of paramagnetism of the substance is described in terms of its magnetic dipole moment. The magnitude of this dipole moment, which is the same for all free radicals containing single electrons, can be calculated, and the value obtained (1.73 Bohr magnetons) has been confirmed experimentally with free radicals in the solid state or at known concentrations in solution. Magnetic susceptibility measurements may be used to demonstrate the existence of free radicals and to measure the position of equilibrium between radicals and their dimers or disproportionation products. Diradicals, with even numbers of electrons, two of which, however, are not paired, are also paramagnetic, the oxygen molecule, O₂, being probably the simplest example of the kind.

The electron paramagnetic-resonance spectra of free radicals provide another technique for their detection and study. According to quantum mechanics, the spin of the odd electron of a free radical, when placed in a magnetic field, may have two, and only two, orientations, one with and the other against the field. These two orientations differ slightly in energy by an amount proportional to the strength of the magnetic field, and the majority of the electrons have the orientation of lower energy. If a system containing free radicals is placed in a magnetic field and exposed to electromagnetic radiation (e.g., in the region of very short radio waves), molecules with the lower energy orientation absorb radiation of a frequency corresponding to an energy just sufficient to flip the odd electron into its higher energy state. This phenomenon gives rise in the simplest case to a paramagnetic-resonance absorption spectrum consisting of a single sharp absorption line. The technique is sensitive and will detect extremely small concentrations of free radicals, as little as one part in 10⁷ having been reported detected. In many organic free radicals, interaction of the odd electron with the magnetic moments of the nuclei of different atoms in the molecule (most commonly with hydrogen nuclei) gives rise to a more complicated system of energy levels and an absorption spectrum consisting of a series of lines. The nature of the spectrum permits the identification of particular free radicals and also gives information about their electronic structure.