Observation of quantum coherence in mesoscopic molecular magnets

By applying a transverse magnetic field B( perpendicular) of sufficient strength to the uniaxial molecular magnets Fe8 and Mn12, the tunneling splitting Delta(t) of their S = +/-10 magnetic ground states can be made large compared to perturbations such as hyperfine and dipolar interactions. We present evidence for such a Delta(t) from magnetic specific heat data below 1 K that is consistent with coherent quantum mechanical tunneling in a "mesoscopic" system under such conditions.     

Specific heat measurements on the site-diluted dipolar ising ferromagnet LiTbpY1−pF4

Specific heat measurements on the diluted dipolar ferromagnet LiTb_pY_1?pF₄ are presented for 0.2?p?1.0. The measured critical temperatures T_c(p) agree with those obtained from previous susceptibility and magnetization measurement. The shape of the specific heat curve is found to be largely influenced by the singlet-singlet separation in the ground state pseudo-doublet, which may explain why below p ≈ 0.325 a λ-anomaly in the specific heat curve can no longer be discerned. For a sample with p = 0.20 we find no evidence of an enhanced nuclear spin ordering, as was suggested by Folkins et al.     

Polysaccharide charge density regulating protein adsorption to air/water interfaces by protein/polysaccharide complex formation

Because the formation of protein/polysaccharide complexes is dominated by electrostatic interaction, polysaccharide charge density is expected to play a major role in the adsorption behavior of the complexes. In this study, pullulan (a non-charged polysaccharide) carboxylated to four different charge densities (fraction of carboxylated subunits: 0.1, 0.26, 0.51, and 0.56) was used to investigate the effect of charge density on the properties of mixed protein/polysaccharide adsorbed layers at air/water interfaces. With all pullulan samples, soluble complexes with beta-lactoglobulin could be formed at low ionic strength, pH 4.5. It was shown that the higher was the pullulan charge density, the more the increase of surface pressure in time was retarded as compared to that for pure beta-lactoglobulin. The retardation was even more pronounced for the development of the dilatational modulus. The lower dilatational modulus can be explained by the ability of the polysaccharides to prevent the formation of a compact protein layer at the air/water interface due to electrostatic repulsion. This ability of the polysaccharides to prevent "layer compactness" increases with the net negative charge of the complexes. If charge density is sufficient (> or = 0.26), polysaccharides may enhance the cohesion between complexes within the adsorbed layer. The charge density of polysaccharides is shown to be a dominant regulator of both the adsorption kinetics as well as the resulting surface rheological behavior of the mixed layers formed. These findings have significant value for the application of complex protein-polysaccharide systems.     

The thermal motion of gold atoms in metal cluster compounds as determined by Mössbauer and specific heat

¹⁹⁷Au Mössbauer effect spectroscopy and specific heat measurements have been performed as a function of temperature on three gold polynuclear cluster compounds, [Au₉(PPh₃)₈](NO₃)₃, Au₁₁(PPh₃)₇(SCN)₃, and Au₅₅(PPh₃)₁₂Cl₆. The Mössbauer data yield information on the vibrational motions of the various distinguishable Au sites, as well as on the motion of the clusters as a whole. The Mössbauer and the specific heat data are successfully described by a superposition of inter- and intra-cluster vibrations. The latter are determined by calculating numerically the normal modes of vibration of the metal cores.     

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.     

Short-range correlations in d-f cyanido-bridged assemblies with XY and XY-Heisenberg anisotropy

Two new d-f cyanido-bridged 1D assemblies [RE(pzam)(3)(H(2)O)Mo(CN)(8)]·H(2)O (RE = Sm(III), Er(III)) were synthesized and their magneto-structural properties have been studied by field-dependent magnetization and specific heat measurements at low temperatures (≥0.3 K). Below ≈ 10 K the ground state of both the Sm(III) and Er(III) ions is found to be a Kramers doublet with effective spin S = 1/2. From analyses of the low-temperature magnetic specific heat and magnetization the exchange coupling between these RE(III) effective spins and the Mo(v) spins S = 1/2 along the structural chains has been determined. It is found to be antiferromagnetic, with J(∥)/k(B) = -2.6 K and Ising-Heisenberg symmetry of the interaction (J(∥)/J(⊥) = 0.3) for RE = Sm(III), whereas the compound with RE = Er(III) behaves as a pure XY chain, with J(⊥)/k(B) = -1.0 K. For the compound [Sm(pzam)(3)(H(2)O)Mo(CN)(8)]·H(2)O a small λ-type anomaly in the specific heat is observed at about 0.6 K, which is ascribed to a transition to long-range magnetic ordering induced by weak interchain interactions of dipolar origin. No evidence for 3D interchain magnetic ordering is found in the Er(III) analogue.