228 research outputs found
Control of oxidation and spin state in a single-molecule junction
The oxidation and spin state of a metal–organic molecule determine its chemical reactivity and magnetic properties. Here, we demonstrate the reversible control of the oxidation and spin state in a single Fe porphyrin molecule in the force field of the tip of a scanning tunneling microscope. Within the regimes of half-integer and integer spin state, we can further track the evolution of the magnetocrystalline anisotropy. Our experimental results are corroborated by density functional theory and wave function theory. This combined analysis allows us to draw a complete picture of the molecular states over a large range of intramolecular deformations
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
Strong Anisotropic Interaction Controls Unusual Sticking and Scattering of CO at Ru(0001)
Lower critical field H_c1 and barriers for vortex entry in Bi_2Sr_2CaCu_2O_{8+delta} crystals
The penetration field H_p of Bi_2Sr_2CaCu_2O_{8+delta} crystals is determined
from magnetization curves for different field sweep rates dH/dt and
temperatures. The obtained results are consistent with theoretical reports in
the literature about vortex creep over surface and geometrical barriers. The
frequently observed low-temperature upturn of H_p is shown to be related to
metastable configurations due to barriers for vortex entry. Data of the true
lower critical field H_c1 are presented. The low-temperature dependence of H_c1
is consistent with a superconducting state with nodes in the gap function.
[PACS numbers: 74.25.Bt, 74.60.Ec, 74.60.Ge, 74.72.Hs
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
Model Exact Low-Lying States and Spin Dynamics in Ferric Wheels; Fe to Fe
Using an efficient numerical scheme that exploits spatial symmetries and
spin-parity, we have obtained the exact low-lying eigenstates of exchange
Hamiltonians for ferric wheels up to Fe. The largest calculation
involves the Fe ring which spans a Hilbert space dimension of about 145
million for M=0 subspace. Our calculated gaps from the singlet ground state
to the excited triplet state agrees well with the experimentally measured
values. Study of the static structure factor shows that the ground state is
spontaneously dimerized for ferric wheels. Spin states of ferric wheels can be
viewed as quantized states of a rigid rotor with the gap between the ground and
the first excited state defining the inverse of moment of inertia. We have
studied the quantum dynamics of Fe as a representative of ferric wheels.
We use the low-lying states of Fe to solve exactly the time-dependent
Schr\"odinger equation and find the magnetization of the molecule in the
presence of an alternating magnetic field at zero temperature. We observe a
nontrivial oscillation of magnetization which is dependent on the amplitude of
the {\it ac} field. We have also studied the torque response of Fe as a
function of magnetic field, which clearly shows spin-state crossover.Comment: Revtex, 24 pages, 8 eps figure
The Role of Structural Flexibility in Plasmon Driven Coupling Reactions Kinetic Limitations in the Dimerization of Nitro Benzenes
Abstract The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4′-dimercaptoazobenzene (DMAB) is a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, structural flexibility is added to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity toward dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer prefers activation of 4NTP over 4NBM. It is concluded that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics
Neel probability and spin correlations in some nonmagnetic and nondegenerate states of hexanuclear antiferromagnetic ring Fe6: Application of algebraic combinatorics to finite Heisenberg spin systems
The spin correlations \omega^z_r, r=1,2,3, and the probability p_N$ of
finding a system in the Neel state for the antiferromagnetic ring Fe(III)6 (the
so-called `small ferric wheel') are calculated. States with magnetization M=0,
total spin 0<=S<=15 and labeled by two (out of four) one-dimensional
irreducible representations (irreps) of the point symmetry group D_6 are taken
into account. This choice follows from importance of these irreps in analyzing
low-lying states in each S-multiplet. Taking into account the Clebsch--Gordan
coefficients for coupling total spins of sublattices (SA=SB=15/2) the global
Neel probability p*_N can be determined. Dependencies of these quantities on
state energy (per bond and in the units of exchange integral J) and the total
spin S are analyzed. Providing we have determined p_N(S) etc. for other
antiferromagnetic rings (Fe10, for instance) we could try to approximate
results for the largest synthesized ferric wheel Fe18. Since thermodynamic
properties of Fe6 have been investigated recently, in the present
considerations they are not discussed, but only used to verify obtained values
of eigenenergies. Numerical results re calculated with high precision using two
main tools: (i) thorough analysis of symmetry properties including methods of
algebraic combinatorics and (ii) multiple precision arithmetic library GMP. The
system considered yields more than 45 thousands basic states (the so-called
Ising configurations), but application of the method proposed reduces this
problem to 20-dimensional eigenproblem for the ground state (S=0). The largest
eigenproblem has to be solved for S=4; its dimension is 60. These two facts
(high precision and small resultant eigenproblems) confirm efficiency and
usefulness of such an approach, so it is briefly discussed here.Comment: 13 pages, 7 figs, 5 tabs, revtex
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