The spin gap in malachite Cu2(OH)2CO3 and its evolution under pressure

Abstract

We report on the microscopic magnetic modeling of the spin-1/2 copper mineral malachite at ambient and elevated pressures. Despite the layered crystal structure of this mineral, the ambient-pressure susceptibility and magnetization data can be well described by an unfrustrated quasi-one-dimensional magnetic model. Weakly interacting antiferromagnetic alternating spin chains are responsible for a large spin gap of 120K. Although the intradimer Cu-O-Cu bridging angles are considerably smaller than the interdimer angles, density functional theory (DFT) calculations revealed that the largest exchange coupling of 190K operates within the structural dimers. The lack of the inversion symmetry in the exchange pathways gives rise to sizable Dzyaloshinskii-Moriya interactions which were estimated by full-relativistic DFT+U calculations. Based on available high-pressure crystal structures, we investigate the exchange couplings under pressure and make predictions for the evolution of the spin gap. The calculations evidence that intradimer couplings are strongly pressure-dependent and their evolution underlies the decrease of the spin gap under pressure. Finally, we assess the accuracy of hydrogen positions determined by structural relaxation within DFT and put forward this computational method as a viable alternative to elaborate experiments.

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Cited by in corpus (19)

• Quantum Magnetism in Minerals
• Frustration and Dzyaloshinsky-Moriya anisotropy in the kagome francisites Cu${}_3$Bi(SeO${}_3{)}_2$O${}_2$X
• Quasi-two-dimensional $S=1/2$ magnetism of Cu[C${}_6$H${}_2$(COO)${}_4$][C${}_2$H${}_5$NH${}_3$]${}_2$
• Frustrated spin chain physics near the Majumdar-Ghosh point in szenicsite Cu${}_3$(MoO${}_4$)(OH)${}_4$
• Quasi-one-dimensional magnetism in the spin-$\frac{1}{2}$ antiferromagnet BaNa${}_2$Cu(VO${}_4$)${}_2$
• Frustration of square cupola in Sr(TiO)Cu${}_4$(PO${}_4$)${}_4$
• Nearly compensated exchange in the dimer compound callaghanite Cu${}_2$Mg${}_2$(CO${}_3$)(OH)${}_6$$\cdot$2H${}_2$O
• Collinear order in a frustrated three-dimensional spin-$\frac{1}{2}$ antiferromagnet Li${}_2$CuW${}_2$O${}_8$
• The magnetic phase diagram of the frustrated spin chain compound linarite, PbCuSO${}_4$(OH)${}_2$, as seen by neutron diffraction and ${}^1$H-NMR
• Low-dimensional magnetism of BaCuTe${}_2$O${}_6$
• Collinear Spin-density-wave Order and Anisotropic Spin Fluctuations in the Frustrated $J_1$--$J_2$ Chain Magnet NaCuMoO${}_4$(OH)
• Highly dispersive magnons with spin-gap like features in the frustrated ferromagnetic S=1/2 chain compound Ca2Y2Cu5O10 detected by inelastic neutron scattering
• The origin of up-up-down-down magnetic order in Cu${}_2$GeO${}_4$
• Frustrated magnetic planes with intricate interaction pathways in the mineral langite Cu${}_4$(OH)${}_6$SO${}_4\cdot 2$H${}_2$O
• Entanglement and quantum correlations in the XX spin-$1/2$ honeycomb lattice
• Role of electronic excitation on the anomalous magnetism of elemental Copper
• Spin excitations in the two-dimensional strongly coupled dimer system malachite
• Kondo-like behavior in a mixed valent oxypnictide $\mathrm{L}{\mathrm{a}}_3\mathrm{C}{\mathrm{u}}_4{\mathrm{P}}_4{\mathrm{O}}_2$
• Pressure-tuned spin chains in brochantite, Cu${}_4$SO${}_4$(OH)${}_6$