A. Lascialfari et al., SPIN DYNAMICS IN MESOSCOPIC SIZE MAGNETIC SYSTEMS - A H-1-NMR STUDY IN RINGS OF IRON(III) IONS, Physical review. B, Condensed matter, 55(21), 1997, pp. 14341-14349
Two magnetic molecular clusters containing almost coplanar rings of ir
on(III) ions with spin S = 5/2 have been investigated by H-1 NMR and r
elaxation measurements. The first system, which will be referred to as
Fe6, is a molecule of general formula [NaFe6(OCH3)(12)(C17O4H15)(6)]ClO4- or [NaFe6(OCH3)(12)(C15H11O2)(6)]+ClO4- or [LiFe6(OCH3)(12)(C15H
11O2)(6)]+ClO4- while the second type of ring, denoted Fe10, correspon
ds to the molecule [Fe-10(OCH3)(20)(C2H2O2Cl)(10)]. The H-1 NMR linewi
dth is broadened by the nuclear dipolar interaction and by the dipolar
coupling of the protons with the iron (III) paramagnetic moment. It i
s found that the nuclear spin-lattice relaxation rate, T-1(-1), of the
proton is a sensitive probe of the Fe spin dynamics. In both clusters
, T-1(-1) decreases with decreasing temperatures from room temperature
, goes through a peak just below about 30 K in Fe6 and 10 K in Fe10, a
nd it drops exponentially to very small values at helium temperature.
The temperature dependence of the relaxation rate is discussed in term
s of the fluctuations of the local spins within the allowed total spin
configurations in the framework of the weak collision theory to descr
ibe the nuclear relaxation. We use the calculated energy levels for th
e Fe6 ring based on a Heisenberg Hamiltonian and the value of J obtain
ed from the fit of the magnetic susceptibility to describe semiquantit
atively the behavior T-1(-1) vs T. The exponential drop of T-1(-1) at
low temperature is consistent with a nonmagnetic singlet ground state
separated by an energy gap from the first excited triplet state. The v
alues obtained for the gap energies are E-T/k = 12 K for Fe10 and E-T/
k = 38 K for Fe6 which are almost twice as big as the values deduced f
rom susceptibility measurements. At all temperatures the relaxation ra
te decreases with increasing magnetic field, i.e., NMR resonance frequ
ency. This effect could be related to the long time persistence of the
spin correlation functions typical of diffusive modes in low dimensio
nal magnetic systems. It is argued that the data presented are a direc
t experimental study of spin dynamics in mesoscopic spin rings and sho
uld afford a test for exact analytical and/or numerical solutions.