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Valerie Marvaud

Publications and source records attributed to Valerie Marvaud.

4 recordsLinked to original sources

A Kinetic Model for Photoswitching of magnetism in the High Spin Molecule [Mo(IV)(CN)2(CN-Cu(II)(tren))6](ClO4)8

The heptanuclear complex [Mo(IV)(CN)2(CN-CuL)6]8+ exhibits photomagnetism. An earlier microscopic model showed that the transition dipole moments for excitation in different spin manifolds are similar in magnitude. In this paper, we attribute photomagnetism to the long lived S=3 charge transfer excited state for which there appears to be sufficient experimental evidence. We model the photomagnetism by employing a kinetic model which includes internal conversions and intersystem crossings. The key feature of the model is assumption of the existence of two kinds of S=3 states: one which has no direct pathway for internal conversion and the other characterized by slow kinetics for internal conversion to the low-energy states. The trapped S=3 state can decay via a thermally activated barrier to the other S=3 state. The experimental temperature dependence of magnetization plot is fitted using rate constants with Arrhenius dependence. The two different experimental cMT vs. T curves obtained with different irradiation times are fitted with our model. Our studies show that the photomagnetism in these systems is governed by kinetics and not due to differences in oscillator strengths for excitation of the different spin states.

cond-mat.str-el

Experimental Estimates of Dephasing Time in Molecular Magnets

Muon spin relaxation measurements in isotropic molecular magnets (MM) with a spin value S ranging from 7/2 to 27/2 are used to determine the magnitude and origin of dephasing time $τ_ϕ$ of molecular magnets. It is found that $τ_ϕ$ ~ 10 nsec with no S or ligand dependence. This indicates a nuclear origin for the stochastic field. Since $τ_ϕ$ is a property of the environment, we argue that it is a number common to similar types of MM. Therefore, $τ_ϕ$ is shorter than the Zener and tunneling times of anisotropic MM such as Fe8 or Mn4 for standard laboratory sweep rates. Our findings call for a stochastic Landau-Zener theory in this particular case.

cond-mat.str-el

Hexacyanometalate Molecular Chemistry : Trinuclear CrNi2 Complexes; MicroSQUID Magnetisation Studies of Intermolecular Interactions

Three different CrNi2 complexes were synthesized. They differ from each other by the nature of the terminal ligand and of the counter anion : [Cr(CN)4[CN-Ni(tetren)]2]Cl, that crystallizes in two different crystallographic systems and [Cr(CN)4[CN-Ni(dienpy2)]2](ClO4). The ground state spin value is 7/2 for the three systems (ferromagnetic interaction between chromium(III) and nickel(II) ions). The magnetisation of the three CrNi2 complexes was measured using an array of micro-SQUIDs in a temperature range between 0.04 K and 7 K, under a magnetic field up to 1 T. The three samples present a three dimensional magnetic ordering. The correlation between the structure and the intermolecular coupling is analysed in terms of steric hindrances of the terminal ligand, orientation of the molecules in the unit cell (canted structure) and crystal symmetry.

cond-mat.mes-hall

Dynamics at T -> 0 in the half-integer isotropic high spin molecules

We investigate the dynamical spin-spin auto-correlation function of the isotropic high spin molecules CrCu$_{6}$ (S=9/2), CrNi$_{6}$ (S=15/2) and CrMn$_{6}$ (S=27/2), using magnetization, $μ$SR and NMR measurements. We find that the field autocorrelation time $τ$ of the molecule's spin at zero and low fields is nearly temperature independent as $T\to 50$ mK. The high temperatures $τ$ is very different between the molecules. Surprisingly, it is identical ($\sim$ 10 nsec) at low temperature. This suggests that $τ$ is governed by hyperfine interactions.

cond-mat.mes-hall