No Arabic abstract
The current efforts to find the materials hosting Kitaev model physics have been focused on Mott insulators of d^5 pseudospin-1/2 ions Ir^{4+} and Ru^{3+} with t_{2g}^5(S=1/2, L=1) electronic configuration. Here we propose that the Kitaev model can be realized in materials based on d^7 ions with t_{2g}^5e_g^2(S=3/2, L=1) configuration such as Co^{2+}, which also host the pseudospin-1/2 magnetism. Considering possible exchange processes, we have derived the d^7 pseudospin-1/2 interactions in 90^{circ} bonding geometry. The obtained Hamiltonian comprises the bond-directional Kitaev K and isotropic Heisenberg J interactions as in the case of d^5 ions. However, we find that the presence of additional, spin-active e_g electrons radically changes the balance between Kitaev and Heisenberg couplings. Most remarkably, we show that the exchange processes involving e_g spins are highly sensitive to whether the system is in Mott (U<Delta) or charge-transfer (U>Delta) insulating regime. In the latter case, to which many cobalt compounds do actually belong, the antiferromagnetic Heisenberg coupling J is strongly suppressed and spin-liquid phase can be stabilized. The results suggest cobalt-based materials as promising candidates for the realization of the Kitaev model.
The realization of Kitaevs honeycomb magnetic model in real materials has become one of the most pursued topics in condensed matter physics and materials science. If found, it is expected to host exotic quantum phases of matter and offers potential realizations of fault$-$tolerant quantum computations. Over the past years, much effort was made on 4d$-$ or 5d$-$ heavy transition metal compounds because of their intrinsic strong spin$-$orbit coupling. But more recently, there have been growing shreds of evidence that the Kitaev model could also be realized in 3d$-$transition metal systems with much weaker spin$-$orbit coupling. This review intends to serve as a guide to this fast$-$developing field focusing on systems with d$^7$ transition metal occupation. It overviews the current theoretical and experimental progress on realizing the Kitaev model in those systems. We examine the recent experimental observations of candidate materials with Co$^{2+}$ ions: e.g., CoPS$_3$, Na$_3$Co$_2$SbO$_6$, and Na$_2$Co$_2$TeO$_6$, followed by a brief review of theoretical backgrounds. We conclude this article by comparing experimental observations with density functional theory (DFT) calculations. We stress the importance of inter$-t_{2g}$ hopping channels and Hunds coupling in the realization of Kitaev interactions in Co$-$based compounds, which has been overlooked in previous studies. This review suggests future directions in the search for Kitaev physics in 3d cobalt compounds and beyond.
The Kitaev model is a rare example of an analytically solvable and physically instantiable Hamiltonian yielding a topological quantum spin liquid ground state. Here we report signatures of Kitaev spin liquid physics in the honeycomb magnet $Li_3Co_2SbO_6$, built of high-spin $it{d^7}$ ($Co^{2+}$) ions, in contrast to the more typical low-spin $it{d^5}$ electron configurations in the presence of large spin-orbit coupling. Neutron powder diffraction measurements, heat capacity, and magnetization studies support the development of a long-range antiferromagnetic order space group of $it{C_C}2/it{m}$, below $it{T_N}$ = 11 K at $it{mu_0H}$ = 0 T. The magnetic entropy recovered between $it{T}$ = 2 K and 50 K is estimated to be 0.6Rln2, in good agreement with the value expected for systems close to a Kitaev quantum spin liquid state. The temperature-dependent magnetic order parameter demonstrates a $beta$ value of 0.19(3), consistent with XY anisotropy and in-plane ordering, with Ising-like interactions between layers. Further, we observe a spin-flop driven crossover to ferromagnetic order with space group of $it{C}2/it{m}$ under an applied magnetic field of $it{mu_0H}$ $approx$ 0.7 T at $it{T}$ = 2 K. Magnetic structure analysis demonstrates these magnetic states are competing at finite applied magnetic fields even below the spin-flop transition. Both the $it{d^7}$ compass model, a quantitative comparison of the specific heat of $Li_3Co_2SbO_6$, and related honeycomb cobaltates to the anisotropic Kitaev model further support proximity to a Kitaev spin liquid state. This material demonstrates the rich playground of high-spin $it{d^7}$ systems for spin liquid candidates, and complements known $it{d^5}$ Ir- and Ru-based materials.
The magnetic system of the pseudobinary compound Mn$_{1-x}$Co$_{x}$Ge has been studied using small-angle neutron scattering and SQUID-measurements. It is found that Mn$_{1-x}$Co$_{x}$Ge orders magnetically at low temperatures in the whole concentration range of $x in [0 div 0.9]$. Three different states of the magnetic structure have been found: a short-periodic helical state at $x leq 0.45$, a long-periodic helical state at $0.45 < x leq 0.8$, and a ferromagnetic state at $x sim 0.9$. Taking into account that the relatively large helical wavevector $k gg 1$ nm$^{-1}$ is characteristic for systems with mainly Ruderman-Kittel-Kasuya-Yoshida (RKKY) interaction, we suggest that the short-periodic helical structure at $x leq 0.45$ is based on an effective RKKY interaction. Also the decay of $k$ with increasing $x$ is ascribed to a reduction of the interaction between second nearest neighbors and, therefore, to an increase of the influence of the Dzyaloshinskiy-Moriya interaction (DMI). As a result of the competition between these two interactions the quantum phase transition from a long-range ordered (LRO) to a short-range ordered (SRO) helical structure has been observed upon increase of the Co-concentration at $x_{c1} sim 0.25$. Further increase of $x$ leads to the appearance of a double peak in the scattering profile at $0.45 < x < 0.7$. The transition from a helical structure to a ferromagnetic state found at $x = 0.9$ is caused by the weakening of DMI as compared to the cubic anisotropy. In summary, the evolution of the magnetic structure of Mn$_{1-x}$Co$_{x}$Ge with increasing $x$ is an example of a continuous transition from a helical structure based on the effective RKKY interaction to a ferromagnetic structure passing through a helical structure based on DMI.
We study the exchange interactions and resulting magnetic phases in the honeycomb cobaltates. For a broad range of trigonal crystal fields acting on Co2+ ions, the low-energy pseudospin-1/2 Hamiltonian is dominated by bond-dependent Ising couplings that constitute the Kitaev model. The non-Kitaev terms nearly vanish at small values of trigonal field Delta, resulting in spin liquid ground state. Considering Na3Co2SbO6 as an example, we find that this compound is proximate to a Kitaev spin liquid phase, and can be driven into it by slightly reducing Delta by sim 20 meV, e.g., via strain or pressure control. We argue that due to the more localized nature of the magnetic electrons in 3d compounds, cobaltates offer the most promising search area for Kitaev model physics.
This paper reviews the current progress on searching the Kitaev spin liquid state in 3d electron systems. Honeycomb cobaltates were recently proposed as promising candidates to realize the Kitaev spin liquid state, due to the more localized wave functions of 3d ions compared with that of 4d and 5d ions, and also the easy tunability of the exchange Hamiltonian in favor of Kitaev interaction. Several key parameters that have large impacts on the exchange constants, such as the charge-transfer gap and the trigonal crystal field, are identified and discussed. Specifically, tuning crystal field effect by means of strain or pressure is emphasized as an efficient phase control method driving the magnetically ordered cobaltates into the spin liquid state. Experimental results suggesting the existence of strong Kitaev interactions in layered honeycomb cobaltates are discussed. Finally, the future research directions are briefly outlined.