Magnetic dipolar ordering and relaxation in the high-spin molecular cluster compound Mn6

Few examples of magnetic systems displaying a transition to pure dipolar magnetic order are known to date, and single-molecule magnets can provide an interesting example. The molecular cluster spins and thus their dipolar interaction energy can be quite high, leading to reasonably accessible ordering temperatures, provided the crystal field anisotropy is sufficiently small. This condition can be met for molecular clusters of sufficiently high symmetry, as for the Mn6 compound studied here. Magnetic specific heat and susceptibility experiments show a transition to ferromagnetic dipolar order at T_{c} = 0.16 K. Classical Monte-Carlo calculations indeed predict ferromagnetic ordering and account for the correct value of T_{c}. In high magnetic fields we detected the contribution of the ^{55}Mn nuclei to the specific heat, and the characteristic timescale of nuclear relaxation. This was compared with results obtained directly from pulse-NMR experiments. The data are in good mutual agreement and can be well described by the theory for magnetic relaxation in highly polarized paramagnetic crystals and for dynamic nuclear polarization, which we extensively review. The experiments provide an interesting comparison with the recently investigated nuclear spin dynamics in the anisotropic single molecule magnet Mn12-ac.Comment: 19 pages, 11 eps figures. Contains extensive discussions on dipolar ordering, specific heat and nuclear relaxation in molecular magnet

Giant isotope effect in the incoherent tunneling specific heat of the molecular nanomagnet Fe8

Time-dependent specific heat experiments on the molecular nanomagnet Fe8 and the isotopic enriched analogue 57Fe8 are presented. The inclusion of the 57Fe nuclear spins leads to a huge enhancement of the specific heat below 1 K, ascribed to a strong increase in the spin-lattice relaxation rate Gamma arising from incoherent, nuclear-spin-mediated magnetic quantum tunneling in the ground-doublet. Since Gamma is found comparable to the expected tunneling rate, the latter process has to be inelastic. A model for the coupling of the tunneling levels to the lattice is presented. Under transverse field, a crossover from nuclear-spin-mediated to phonon-induced tunneling is observed.Comment: Replaced with version accepted for publication in Physical Review Letter

Magnetic long-range order induced by quantum relaxation in single-molecule magnets

Can magnetic interactions between single-molecule magnets (SMMs) in a crystal establish long-range magnetic order at low temperatures deep in the quantum regime, where the only electron spin-fluctuations are due to incoherent magnetic quantum tunneling (MQT)? Put inversely: can MQT provide the temperature dependent fluctuations needed to destroy the ordered state above some finite Tc, although it should basically itself be a T-independent process? Our experiments on two novel Mn4 SMMs provide a positive answer to the above, showing at the same time that MQT in the SMMs has to involve spin-lattice coupling at a relaxation rate equaling that predicted and observed recently for nuclear spin-mediated quantum relaxation.Comment: 4 pages, 3 figure

Long-range ferromagnetic dipolar ordering of high-spin molecular clusters

We report the first example of a transition to long-range magnetic order in a purely dipolarly interacting molecular magnet. For the magnetic cluster compound Mn6O4Br4(Et2dbm)6, the anisotropy experienced by the total spin S=12 of each cluster is so small that spin-lattice relaxation remains fast down to the lowest temperatures, thus enabling dipolar order to occur within experimental times at Tc = 0.16 K. In high magnetic fields, the relaxation rate becomes drastically reduced and the interplay between nuclear- and electron-spin lattice relaxation is revealed.Comment: 4 pages, 4 .eps figures; accepted for publication in Phys. Rev. Let

Magnetothermal properties of molecule-based materials

We critically review recent results obtained by studying the low-temperature specific heat of some of the most popular molecular magnets. Perspectives of this field are discussed as well.Comment: 12 pages text + 14 pages figures, Submitted as "feature article" to Journal of Materials Chemistr

Quantum nanomagnets and nuclear spins: an overview

This mini-review presents a simple and accessible summary on the fascinating physics of quantum nanomagnets coupled to a nuclear spin bath. These chemically synthesized systems are an ideal test ground for the theories of decoherence in mesoscopic quantum degrees of freedom, when the coupling to the environment is local and not small. We shall focus here on the most striking quantum phenomenon that occurs in such nanomagnets, namely the tunneling of their giant spin through a high anisotropy barrier. It will be shown that perturbative treatments must be discarded, and replaced by a more sophisticated formalism where the dynamics of the nanomagnet and the nuclei that couple to it are treated together from the beginning. After a critical review of the theoretical predictions and their experimental verification, we continue with a set of experimental results that challenge our present understanding, and outline the importance of filling also this last gap in the theory.Comment: 14 pages, 3 figures. Chapter in the Proceedings of the 2006 Les Houches summer school "Quantum Magnetism", ed. B. Barbara & Y. Imry, Springer (2007

Long-range ferromagnetic dipolar ordering of high-spin molecular clusters

We report the first example of a transition to long-range magnetic order in a purely dipolarly interacting molecular magnet. For the magnetic cluster compound Mn6O4Br4(Et2dbm)6, the anisotropy experienced by the total spin S=12 of each cluster is so small that spin-lattice relaxation remains fast down to the lowest temperatures, thus enabling dipolar order to occur within experimental times at Tc=0.16 K. In high magnetic fields, the relaxation rate becomes drastically reduced and the interplay between nuclear- and electron-spin lattice relaxation is revealed

Magnetic dipolar ordering and relaxation in the high-spin molecular cluster compound Mn6

Few examples of magnetic systems displaying a transition to pure dipolar magnetic order are known to date. As was recently shown, within the newly discovered class of single-molecule magnets, quite attractive examples of dipolar magnetism may be found. The molecular cluster spins and thus their dipolar interaction energy can be quite high, leading to reasonably accessible ordering temperatures even for sizable intercluster distances. In favorable cases bonding between clusters in the molecular crystal is by van der Waals forces only, and no exchange paths of importance can be distinguished. An important restriction, however, is the requirement of sufficiently low crystal field anisotropy for the cluster spin, in order to prevent the occurrence of superparamagnetic blocking at temperatures above the dipolar ordering transition. This condition can be met for molecular clusters of sufficiently high symmetry, as for the Mn6 molecular cluster compound studied here. The uniaxial anisotropy of the cluster spin S=12 is as small as D/kB=0.013 K, giving a total zero-field splitting of the S=12 multiplet of 1.9 K. As a result, the electron-spin lattice relaxation time remains fast (~10–4 s) down to Tc and no blocking occurs. Magnetic specific heat and susceptibility experiments show a transition to ferromagnetic dipolar order at Tc=0.16 K. Classical Monte Carlo calculations, performed for Ising S=12 dipoles on a lattice do predict ferromagnetic ordering and account for the value of Tc as well as the shape of the observed specific heat anomaly. By applying magnetic fields up to 6 T the hyperfine contributions Chf to the specific heat arising from the 55Mn nuclei could be detected. From the time dependence of the measured Chf the nuclear-spin lattice relaxation time T1n could be determined for the same field range in the temperature region 0.2<T<0.6 K. The nuclear magnetic relaxation was further studied by high field 55Mn pulse NMR measurements of both the nuclear T1n and T2n at T=0.9 K (up to 7 T). The data are in good mutual agreement and can be well described by the theory for magnetic relaxation in highly polarized paramagnetic crystals and for dynamic nuclear polarization, which we extensively review. The experiments provide an interesting comparison with the recently investigated nuclear spin dynamics in the anisotropic single-molecule magnet Mn12-a

Magnetic long-range order induced by quantum ralaxation in single-molecule magnets

Can magnetic interactions between single-molecule magnets (SMMs) in a crystal establish long-range magnetic order at low temperatures deep in the quantum regime, where the only electron spin fluctuations are due to incoherent magnetic quantum tunneling (MQT)? Put inversely: can MQT provide the temperature dependent fluctuations needed to destroy the ordered state above some finite Tc, although it should basically itself be a T-independent process? Our experiments on two novel Mn4 SMMs provide a positive answer to the above, showing at the same time that MQT in the SMMs has to involve spin-lattice coupling at a relaxation rate equaling that predicted and observed recently for nuclear-spin-mediated quantum relaxation