All nucleons, that is neutrons and protons, composing any atomic nucleus, have the intrinsic quantum property of spin, an intrinsic angular momentum analogous to the classical angular momentum of a spinning sphere. The overall spin of the nucleus is determined by the spin quantum number S. If the numbers of both the protons and neutrons in a given nuclide are even then , i.e. there is no overall spin. Then, just as electrons pair up in nondegenerate atomic orbitals, so do even numbers of protons or even numbers of neutrons (both of which are also spin- particles and hence fermions), giving zero overall spin.
However, a proton and neutron spin vector that aligns itself opposite to the external magnetic field vector will have a lower energy when their spins are parallel, not anti-parallel. This parallel spin alignment of distinguishable particles does not violate the Pauli exclusion principle. The lowering of energy for parallel spins has to do with the quark structure of these two nucleons. As a result, the spin ground state for the deuteron (the nucleus of deuterium, the H isotope of hydrogen), which has only a proton and a neutron, corresponds to a spin value of 1, not of zero. On the other hand, because of the Pauli exclusion principle, the tritium isotope of hydrogen must have a pair of anti-parallel spin neutrons (of total spin zero for the neutron-spin pair), plus a proton of spin . Therefore, the tritium total nuclear spin value is again , just like for the simpler, abundant hydrogen isotope, H nucleus (the proton). The NMR absorption frequency for tritium is also similar to that of H. In many other cases of non-radioactive nuclei, the overall spin is also non-zero. For example, the  nucleus has an overall spin value .
A non-zero spin  is always associated with a non-zero magnetic dipole moment, , via the relation  where γ is the gyromagnetic ratio. Classically, this corresponds to the proportionality between the angular momentum and the magnetic dipole moment of a spinning charged sphere, both of which are vectors parallel to the rotation axis whose length increases proportional to the spinning frequency. It is the magnetic moment and its interaction with magnetic fields that allows the observation of NMR signal associated with transitions between nuclear spin levels during resonant RF irradiation or caused by Larmor precession of the average magnetic moment after resonant irradiation. Nuclides with even numbers of both protons and neutrons have zero nuclear magnetic dipole moment and hence do not exhibit NMR signal. For instance,  is an example of a nuclide that produces no NMR signal, whereas , ,  and  are nuclides that do exhibit NMR spectra. The last two nuclei have spin S >  and are therefore quadrupolar nuclei.
Electron spin resonance (ESR) is a related technique in which transitions between electronic rather than nuclear spin levels are detected. The basic principles are similar but the instrumentation, data analysis, and detailed theory are significantly different. Moreover, there is a much smaller number of molecules and materials with unpaired electron spins that exhibit ESR (or electron paramagnetic resonance (EPR)) absorption than those that have NMR absorption spectra. On the other hand, ESR has much higher signal per spin than NMR does.