288 research outputs found
Butterfly hysteresis loop at non-zero bias field in antiferromagnetic molecular rings: cooling by adiabatic magnetization
At low temperatures, the magnetization of the molecular ferric wheel NaFe
exhibits a step at a critical field due to a field-induced
level-crossing. By means of high-field torque magnetometry we observed a
hysteretic behavior at the level-crossing with a characteristic butterfly shape
which is analyzed in terms of a dissipative two-level model. Several unusual
features were found. The non-zero bias field of the level-crossing suggests the
possibility of cooling by adiabatic magnetization.Comment: 4 pages, 5 figures, REVTEX4, to appear in PR
Ferromagnetic coupling and magnetic anisotropy in molecular Ni(II) squares
We investigated the magnetic properties of two isostructural Ni(II) metal
complexes [Ni4Lb8] and [Ni4Lc8]. In each molecule the four Ni(II) centers form
almost perfect regular squares. Magnetic coupling and anisotropy of single
crystals were examined by magnetization measurements and in particular by
high-field torque magnetometry at low temperatures. The data were analyzed in
terms of an effective spin Hamiltonian appropriate for Ni(II) centers. For both
compounds, we found a weak intramolecular ferromagnetic coupling of the four
Ni(II) spins and sizable single-ion anisotropies of the easy-axis type. The
coupling strengths are roughly identical for both compounds, whereas the
zero-field-splitting parameters are significantly different. Possible reasons
for this observation are discussed.Comment: 7 pages, 7 figure
Hierarchical assembly of discrete copper(ii) metallo-structures from pre-assembled dinuclear (bis-beta-diketonato)metallocycles and flexible difunctional co-ligands
The sequential interaction of preformed [Cu(L) (THF)] (where HL is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu (L)]·2HO (where H L is 1,1-(4,4′-oxybiphenylene)-bis(4,4- dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N′- dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu(L)(mpip)] ·2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu(L)} (dmpip)]·2dmpip. In contrast, dinuclear [Cu (L)(dmpip)]·dmpip and [{Cu(L)}(thiomorph) ]·3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu(L)(THF) ]·2THF and Cu(L)(mpip) ]·HO incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4′-linked phenylene rings of H L results in generation of a dinuclear [Cu L] species rather than a trinuclear (triangular) [CuL] species of the type formed by the more rigid bis-β-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4′ positions
Electronic structure study by means of X-ray spectroscopy and theoretical calculations of the "ferric star" single molecule magnet
The electronic structure of the single molecule magnet system
M[Fe(L)2]3*4CHCl3 (M=Fe,Cr; L=CH3N(CH2CH2O)2) has been studied using X-ray
photoelectron spectroscopy, X-ray absorption spectroscopy, soft X-ray emission
spectroscopy, and density functional calculations. There is good agreement
between theoretical calculations and experimental data. The valence band mainly
consists of three bands between 2 eV and 30 eV. Both theory and experiments
show that the top of the valence band is dominated by the hybridization between
Fe 3d and O 2p bands. From the shape of the Fe 2p spectra it is argued that Fe
in the molecule is most likely in the 2+ charge state. Its neighboring atoms
(O,N) exhibit a magnetic polarisation yielding effective spin S=5/2 per iron
atom, giving a high spin state molecule with a total S=5 effective spin for the
case of M = Fe.Comment: Fig.2 replaced as it will appear in J. Chem. Phy
Condensed-phase isomerization through tunnelling gateways
Quantum mechanical tunnelling describes transmission of matter waves through a barrier with height larger than the energy of the wave. Tunnelling becomes important when the de Broglie wavelength of the particle exceeds the barrier thickness; because wavelength increases with decreasing mass, lighter particles tunnel more efficiently than heavier ones. However, there exist examples in condensed-phase chemistry where increasing mass leads to increased tunnelling rates. In contrast to the textbook approach, which considers transitions between continuum states, condensed-phase reactions involve transitions between bound states of reactants and products. Here this conceptual distinction is highlighted by experimental measurements of isotopologue-specific tunnelling rates for CO rotational isomerization at an NaCl surface, showing nonmonotonic mass dependence. A quantum rate theory of isomerization is developed wherein transitions between sub-barrier reactant and product states occur through interaction with the environment. Tunnelling is fastest for specific pairs of states (gateways), the quantum mechanical details of which lead to enhanced cross-barrier coupling; the energies of these gateways arise nonsystematically, giving an erratic mass dependence. Gateways also accelerate ground-state isomerization, acting as leaky holes through the reaction barrier. This simple model provides a way to account for tunnelling in condensed-phase chemistry, and indicates that heavy-atom tunnelling may be more important than typically assumed
Structure and Reactivity of α-Al<sub>2</sub>O<sub>3</sub>(0001) Surfaces: How Do Al-I and Gibbsite-like Terminations Interconvert?
The α-Al2O3(0001) surface has been extensively studied because of its significance in both fundamental research and application. Prior work suggests that in ultra-high-vacuum (UHV), in the absence of water, the so-called Al–I termination is thermodynamically favored, while in ambient, in contact with liquid water, a Gibbsite-like layer is created. While the view of the α-Al2O3(0001)/H2O(l) interface appears relatively clear in theory, experimental characterization of this system has resulted in estimates of surface acidity, i.e., isoelectric points, that differ by 4 pH units and surface structure that in some reports has non-hydrogen-bonded surface aluminol (Al–OH) groups and in others does not. In this study, we employed vibrational sum frequency spectroscopy (VSFS) and density functional theory (DFT) simulation to study the surface phonon modes of the differently terminated α-Al2O3(0001) surfaces in both UHV and ambient. We find that, on either water dosing of the Al–I in UHV or heat-induced dehydroxylation of the Gibbsite-like in ambient, the surfaces do not interconvert. This observation offers a new explanation for disagreements in prior work on the α-Al2O3(0001)/liquid water interface─different preparation methods may create surfaces that do not interconvert─and shows that the surface phonon spectral response offers a novel probe of interfacial hydrogen bonding structure
Strong Anisotropic Interaction Controls Unusual Sticking and Scattering of CO at Ru(0001)
Quantum size effects in Pb islands on Cu(111): Electronic-structure calculations
The appearance of "magic" heights of Pb islands grown on Cu(111) is studied
by self-consistent electronic structure calculations. The Cu(111) substrate is
modeled with a one-dimensional pseudopotential reproducing the essential
features, i.e. the band gap and the work function, of the Cu band structure in
the [111] direction. Pb islands are presented as stabilized jellium overlayers.
The experimental eigenenergies of the quantum well states confined in the Pb
overlayer are well reproduced. The total energy oscillates as a continuous
function of the overlayer thickness reflecting the electronic shell structure.
The energies for completed Pb monolayers show a modulated oscillatory pattern
reminiscent of the super-shell structure of clusters and nanowires. The energy
minima correlate remarkably well with the measured most probable heights of Pb
islands. The proper modeling of the substrate is crucial to set the
quantitative agreement.Comment: 4 pages, 4 figures. Submitte
Spin dynamics in molecular ring nanomagnets: Significant effect of acoustic phonons and magnetic anisotropies
The nuclear spin-lattice relaxation rate 1/T_1_ is calculated for magnetic
ring clusters by fully diagonalizing their microscopic spin Hamiltonians.
Whether the nearest-neighbor exchange interaction J is ferromagnetic or
antiferromagnetic, 1/T_1_ versus temperature T in ring nanomagnets may be
peaked at around k_B_T=|J| provided the lifetime broadening of discrete energy
levels is in proportion to T^3^. Experimental findings for ferromagnetic and
antiferromagnetic Cu^II^ rings are reproduced with crucial contributions of
magnetic anisotropies as well as acoustic phonons.Comment: 5 pages with 5 figures embedded, to be published in J. Phys. Soc.
Jpn. 75, No. 10 (2006
Magnetic Anisotropy in the Molecular Complex V15
We apply degenerate perturbation theory to investigate the effects of
magnetic anisotropy in the magnetic molecule V15. Magnetic anisotropy is
introduced via Dzyaloshinskii-Moriya (DM) interaction in the full Hilbert space
of the system. Our model provides an explanation for the rounding of
transitions in the magnetization as a function of applied field at low
temperature, from which an estimate for the DM interaction is found. We find
that the calculated energy differences of the lowest energy states are
consistent with the available data. Our model also offers a novel explanation
for the hysteretic nature of the time-dependent magnetization data.Comment: Final versio
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