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Quasi-two-dimensional $S=1/2$ magnetism of Cu[C$_6$H$_2$(COO)$_4$][C$_2$H$_5$NH$_3$]$_2$

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 Added by Ramesh Chandra Nath
 Publication date 2014
  fields Physics
and research's language is English




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We report structural and magnetic properties of the spin-$frac12$ quantum antiferromagnet Cu[C$_6$H$_2$(COO)$_4$][C$_2$H$_5$NH$_3$]$_2$ by means of single-crystal x-ray diffraction, magnetization, heat capacity, and electron spin resonance (ESR) measurements on polycrystalline samples, as well as band-structure calculations. The triclinic crystal structure of this compound features CuO$_4$ plaquette units connected into a two-dimensional framework through anions of the pyromellitic acid [C$_6$H$_2$(COO)$_4$]$^{4-}$. The ethylamine cations [C$_2$H$_5$NH$_3]^+$ are located between the layers and act as spacers. Magnetic susceptibility and heat capacity measurements establish a quasi-two-dimensional, weakly anisotropic and non-frustrated spin-$frac12$ square lattice with the ratio of the couplings $J_a/J_csimeq 0.7$ along the $a$ and $c$ directions, respectively. No clear signatures of the long-range magnetic order are seen in thermodynamic measurements down to 1.8,K. However, the gradual broadening of the ESR line suggests that magnetic ordering occurs at lower temperatures. Leading magnetic couplings are mediated by the organic anion of the pyromellitic acid and exhibit a non-trivial dependence on the Cu--Cu distance, with the stronger coupling between those Cu atoms that are further apart.



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We report the crystal growth and structural and magnetic properties of quasi two-dimensional $S=1/2$ quantum magnet Cu[C$_6$H$_2$(COO)$_4$][H$_3$N-(CH$_2$)$_2$-NH$_3$]$cdot$3H$_2$O. It is found to crystallize in a monoclinic structure with space group $C2/m$. The CuO$_4$ plaquettes are connected into a two-dimensional framework in the $ab$-plane through the anions of [C$_6$H$_2$(COO)$_4$]$^{4-}$ (pyromellitic acid). The [H$_3$N-(CH$_2$)$_2$-NH$_3$]$^{2+}$$cdot$3H$_2$O groups are located between the layers and provide a weak interlayer connection via hydrogen (H...O) bonds. The temperature dependent magnetic susceptibility is well described by $S=1/2$ frustrated square lattice ($J_1-J_2$) model with nearest-neighbor interaction $J_1/k_{rm B} simeq 5.35$ K and next-nearest-neighbor interaction $J_2/k_{rm B} simeq -0.01$ K. Even, our analysis using frustrated rectangular lattice ($J_{1a,b}-J_2$) model confirms almost isotropic nearest-neighbour interactions ($J_{rm 1a}/k_{rm B} simeq 5.31$ K and $J_{rm 1b}/k_{rm B} simeq 5.38$ K) in the $ab$-plane and $J_2/k_{rm B}simeq-0.24$ K. Further, the isothermal magnetization at $T=1.9$ K is also well described by a non-frustrated square lattice model with $J_1/k_{rm B} simeq 5.2$ K. Based on the $J_2/J_1$ ratio, the compound can be placed in the N{e}el antiferromagnetic state of the $J_1 - J_2$ phase diagram. No signature of magnetic long-range-order was detected down to 2 K.
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Specific heat measurements down to 0.5 K have been performed on a single crystal sample of a spin-ladder like compound Cu$_{2}$(C$_{5}$H$_{12}$N$_{2}$)$_{2}$Cl$_{4}$ under magnetic fields up to 12 T. The temperature dependence of the observed data in a magnetic field below 6 T is well reproduced by numerical results calculated for the S=1/2 two-leg ladder with $J_{rm{rung}}$/$J_{rm{leg}}$=5. In the gapless region above 7 T ($H_{rm{c1}}$), the agreement between experiment and calculation is good above about 2 K and a sharp and a round peak were observed below 2 K in a magnetic field around 10 T, but the numerical data show only a round peak, the magnitude of which is smaller than that of the observed one. The origin of the sharp peak and the difference between the experimental and numerical round peak are discussed.
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