Electron paramagnetic resonance

Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford. Every electron has a magnetic moment and spin quantum number , with magnetic components or . In the presence of an external magnetic field with strength , the electron's magnetic moment aligns itself either antiparallel () or parallel () to the field, each alignment having a specific energy due to the Zeeman effect: where is the electron's so-called g-factor (see also the Landé g-factor), for the free electron, is the Bohr magneton. Therefore, the separation between the lower and the upper state is for unpaired free electrons. This equation implies (since both and are constant) that the splitting of the energy levels is directly proportional to the magnetic field's strength, as shown in the diagram below. An unpaired electron can change its electron spin by either absorbing or emitting a photon of energy such that the resonance condition, , is obeyed. This leads to the fundamental equation of EPR spectroscopy: . Experimentally, this equation permits a large combination of frequency and magnetic field values, but the great majority of EPR measurements are made with microwaves in the 9000–10000 MHz (9–10 GHz) region, with fields corresponding to about 3500 G (0.35 T). Furthermore, EPR spectra can be generated by either varying the photon frequency incident on a sample while holding the magnetic field constant or doing the reverse. In practice, it is usually the frequency that is kept fixed.