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Rafael Calvo

Publications and source records attributed to Rafael Calvo.

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Temperature Dependence of the Effective Interdimeric Exchange Interaction in a Weakly Coupled Antiferromagnetic Dimeric Copper Compound

We report a variation with temperature ($T$) of the effective interdimeric interaction $J^\prime_{\mathrm{eff}}$ in the antiferromagnetic (AFM) copper dimeric organic compound Cu$_2$[TzTs]$_4$ [N-thiazol-2-yl-toluenesulfonamidate Cu$^\mathrm{II}$]. This $T$ dependence was obtained from measurements of the effects in the electron paramagnetic resonance (EPR) spectra of the proposed quantum phase transition associated to the exchange narrowing processes. Cu$_2$[TzTs]$_4$ contains exchange coupled pairs of Cu$^\mathrm{II}$ spins $\mathbf{S_\mathrm{A}}$ and $\mathbf{S_\mathrm{B}}$ ($S$ = 1/2), with intradimeric AFM exchange coupling $J_0$ = (-115$\pm$1) cm$^{-1}$ ($\mathcal{H}_\mathrm{ex} = -J_\mathrm{0} \mathbf{S_\mathrm{A}}\cdot \mathbf{S_\mathrm{B}}$). The variation of the EPR line width of single crystals with field orientation around a "magic angle" where the transitions intersect, as well as the integrated signal intensity of the so-called "U-peak" of the powder spectrum were measured as a function of $T$. Modeling these data using arguments of exchange narrowing in the adiabatic regime considering the angular variation of the single crystal spectra and a geometric description, we find that $|J^\prime_{\mathrm{eff}}|$ associated with the exchange frequency $ω_{ex}$ is negligible for $T<<|J_\mathrm{0}/k_\mathrm{B}|$, when the units are uncoupled, and $|J^\prime_{\mathrm{eff}}|$ = (0.080 $\pm$ 0.005) cm$^{-1}$ ($|J^\prime_{\mathrm{eff}}/J_0|$ = 7.0$\times$10$^{-4}$) at 298 K. Within this $T$-interval, two ranges of $J^\prime_{\mathrm{eff}}$ with linear temperature variation but different slopes, with a kink at $\sim$80 K, are observed and discussed. This $T$-dependence arises from the growing population of the triplet state and its relevance in the properties of various arrays of DUs is discussed. Our experimental procedures and results are compared with those of previous works.

cond-mat.other

Antiferromagnetic spin chain behavior and a transition to 3D magnetic order in Cu(D,L-alanine)2: Roles of H-bonds

We study the spin chain behavior, a transition to 3D magnetic order and the magnitudes of the exchange interactions for the metal-amino acid complex Cu(D,L-alanine)2.H2O, a model compound to investigate exchange couplings supported by chemical paths characteristic of biomolecules. Thermal and magnetic data were obtained as a function of temperature (T) and magnetic field (B0). The magnetic contribution to the specific heat, measured between 0.48 and 30 K, displays above 1.8 K a 1D spin-chain behavior that can be fitted with an intrachain antiferromagnetic (AFM) exchange coupling constant 2J0 = (-2.12 $\pm$ 0.08) cm$^{-1}$, between neighbor coppers at 4.49 Å along chains connected by non-covalent and H-bonds. We also observe a narrow specific heat peak at 0.89 K indicating a phase transition to a 3D magnetically ordered phase. Magnetization curves at fixed T = 2, 4 and 7 K with B0 between 0 and 9 T, and at T between 2 and 300 K with several fixed values of B0 were globally fitted by an intrachain AFM exchange coupling constant 2J0 = (-2.27 $\pm$ 0.02) cm$^{-1}$ and g = 2.091 $\pm$ 0.005. Interchain interactions J1 between coppers in neighbor chains connected through long chemical paths with total length of 9.51 Å are estimated within the range 0.1 < |2J1| < 0.4 cm$^{-1}$, covering the predictions of various approximations. We analyze the magnitudes of 2J0 and 2J1 in terms of the structure of the corresponding chemical paths. The main contribution in supporting the intrachain interaction is assigned to H-bonds while the interchain interactions are supported by paths containing H-bonds and carboxylate bridges, with the role of the H-bonds being predominant. We compare the obtained intrachain coupling with studies of compounds showing similar behavior and discuss the validity of the approximations allowing to calculate the interchain interactions.

cond-mat.mes-hall