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The sensitivity of the EPR method (i.e., the minimal number of detectable spins , the implication is that the ratio of the unpaired electron's spin magnetic moment to its angular momentum differs from the free-electron value.Since an electron's spin magnetic moment is constant (approximately the Bohr magneton), then the electron must have gained or lost angular momentum through spin–orbit coupling.The principal axes of this tensor are determined by the local fields, for example, by the local atomic arrangement around the unpaired spin in a solid or in a molecule.Choosing an appropriate coordinate system (say, x,y,z) allows one to "diagonalize" this tensor, thereby reducing the maximal number of its components from 9 to 3: g are the components of the magnetic field vector in the coordinate system (x,y,z); their magnitudes change as the field is rotated, so does the frequency of the resonance.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.

Since the source of an EPR spectrum is a change in an electron's spin state, the EPR spectrum for a radical (S = 1/2 system) would consist of one line.At this point the unpaired electrons can move between their two spin states.Since there typically are more electrons in the lower state, due to the Maxwell–Boltzmann distribution (see below), there is a net absorption of energy, and it is this absorption that is monitored and converted into a spectrum.Greater complexity arises because the spin couples with nearby nuclear spins.The magnitude of the coupling is proportional to the magnetic moment of the coupled nuclei and to the mechanism of the coupling.

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