Abstract
To understand what electron nuclear double resonance (ENDOR) transitions are, let us consider the energy levels of a system containing one unpaired electron (S = ½) and one nuclear spin (I = ½), as in a hydrogen atom. Since the electron spin and nuclear spin can each be oriented with or against the external magnetic field, there are four possible energy levels as shown in Figure 4.1. The two electron spin eigenfunctions are denoted by αe and βe, whereas the two nuclear spin wavefunctions are denoted αn and βn. In the presence of a large external applied field, the selection rule in electron paramagnetic resonance (EPR) is that the electron flips (changes directions) but the nuclear spin does not flip in an EPR transition. Thus, in Figure 4.1, an EPR transition will occur between energy levels 1 and 4 and a second EPR transitions will occur between energy levels 2 and 3. The intensity of the transition between energy levels 1 and 4 will depend on the population differences of these two energy levels. If one then applies a nuclear frequency to the system, which corresponds to either the energy difference between levels 4 and 3 or the difference between lines 2 and 1, one will induce nuclear spin flip that will change the populations in energy levels 4 and 1, respectively. This changes the intensity of the observed EPR signal. This change in intensity is referred to as the ENDOR response.
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Kispert, L.D., Piekara-Sady, L. (2006). ENDOR SPECTROSCOPY. In: Vij, D. (eds) Handbook of Applied Solid State Spectroscopy. Springer, Boston, MA. https://doi.org/10.1007/0-387-37590-2_4
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