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We have studied the nuclear modulation effect in the electron spin echo decay envelope for the complexes Cu2+–ethylenediamine–imidazole and Cu2+– (imidazole)4 with specific attention to the prominent low frequency patterns due to coupling between Cu2+ and the remote nitrogen nucleus of bound imidazole. (Nitrogen nuclei directly coordinated with Cu2+ do not contribute to the effect.) Some experiments were also made with 15N substituted imidazole in order to distinguish between contributions due to the electron nuclear coupling and to the quadrupolar interaction of 14N. Complexes involving Cu2+ and imidazole were selected for study because of their common occurrence in copper proteins. It was found that the remote nitrogen of imidazole is coupled to Cu2+ by a pseudodipolar term which is several times larger than the classical dipolar coupling and which can be represented by assigning an effective radial distance reff=2.9 Å to the nitrogen nucleus in place of the actual physical distance r=4.16 Å. There is also a contact term AI⋅S, where A=1.75 MHz for 14N (A=2.5 MHz for 15N). The magnitude of this contact term is such that, when the electron spin echo experiments are performed in the X-band range (i.e., at fields?3 kG), it almost cancels the Zeeman term for one of the MS=±1/2 manifolds, thus permitting the observation of the zero field quadrupolar frequencies of 14N in the echo envelope. These frequencies are substantially the same as those reported by Hunt, Mackay, and Edmonds (Ref. 21) for the protonated nitrogen in imidazole, thus showing that the imidazole ligands are protonated and that the two complexes studied here carry a net positive charge of 2. Computer simulations of the two-pulse echo envelope have been made in order to obtain an estimate for the pseudodipolar interaction, and in order to establish that the mixture of 14N (or 15N) superhyperfine states is such as to yield modulation patterns of approximately the observed depths.

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The electron-spin-echo phase memory TM has been studied both experimentally and theoretically for the specific case in which it is limited by the lattice relaxation processes occurring in the sample. The relevant mechanism is as follows. Lattice relaxation of any spins, whether or not they belong to the species being observed, causes fluctuations in the local fields and so destroys the relations between precessional phases which lead to the generation of echoes. The effect of these fluctuations on the echo amplitude can be calculated by taking an ensemble average for the precessing spins and for all the environmental spins which give rise to significant time variations of the local fields in the sample. The problem reduces to that of finding a time and a space average. The space average has been obtained here by assuming a random distribution of spins in the paramagnetic sample, and by applying the statistical methods of Margenau. In order to obtain the time average, two models have been chosen to represent the time variation of the components n z for the relaxing spins. In one model, the ii z are treated as Gaussian random variables (Gauss-Markoff model), and in the other the spins are assumed to make sudden jumps at random times between the "spin-up" and "spin-down" quantum states (sudden-jump model). Different forms of echo envelope are derived for the two models. Further differences in behavior will be observed, according to whether the sample is singly or doubly doped. If the sample contains only one spin species, T M becames shorter as the temperature is raised and as the lattice relaxation time T\ is reduced. Initially, TM is limited by local field fluctuations and may be considerably shorter than T\. Eventually, as the lattice relaxation of the precessing spins themselves becomes the dominant factor, T\ and TM tend to the same value. If the sample contains two species A and B, where B relaxes more rapidly than A, then T M (A) and TM(B) both begin by shortening as Ti(B) is reduced. For very small values of Ti(B), however, T M (A) lengthens again.The rapidly fluctuating local fields due to the 5-spins produce a diminishing effect on the A spins, the phenomenon being analogous to motional narrowing. The form of the A -spin echo envelope in the limit of rapid .S-spin relaxation does not depend on the model chosen to represent the time variation of fi 2 during the relaxation of the B spins.Experimental results are presented for two-pulse and three-pulse echoes, and are compared with the calculations. The material is CaW0 4 doped with Ce and Er or with Mn and Er. At the lower temperatures, the results are in moderately good agreement with the Gauss-Markoff theory. At higher temperatures, the results can only be explained by assuming that the transition rate between the levels of the Er ground doublet is an order of magnitude higher than the transition rate inferred from T\ measurements. It is tentatively suggested that this may arise from the fact that TM depends on the arithmetic sum of the upward and downward...

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