arXiv subjects

C. Koo

Publications and source records attributed to C. Koo.

13 recordsLinked to original sources

arXiv2025

The Relevance of Non-axiality and Low-lying Excited States for Slow Magnetic Relaxation in Pentagonal-bipyramidal Erbium(III) Complexes Probed by High-frequency EPR

High-frequency/high-field electron paramagnetic resonance studies on a series of seven-coordinate pentagonal-bipyramidal (PBP) erbium(III) complexes Er(DAPMBH/H$_2$DAPS)X (H$_2$DAPMBH = 2,6-diacetylpyridine bis-4-methoxy benzoylhydrazone, H$_4$DAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) demonstrate the effects of different apical ligands (X = (H$_2$O)Cl (1), (CH$_3$OH)N$_3$ (2), Cl$_2$ (3)) on the local magnetic anisotropy of the central Er(III) ions. In particular, we report direct experimental determination of the effective $g$-values and zero field splittings of the energetically low-lying Kramers doublets. Our quantitative determination of the magnetic anisotropy highlights the relevance of an axial $g$-tensor for SMM behaviour and suggests that fast magnetic relaxation is mainly driven by a thermally assisted quantum tunnelling process via low-lying excited states.

cond-mat.str-el↗

arXiv2021

Exceptional field dependence of antiferromagnetic magnons in LiFePO$_4$

Low-energy magnon excitations in magnetoelectric LiFePO$_4$ have been investigated by high-frequency high-field electron spin resonance spectroscopy in magnetic fields up to B = 58 T and frequencies up to f = 745 GHz. For magnetic fields applied along the easy magnetic axis, the excitation gap softens and vanishes at the spin-flop field of BSF = 32 T before hardening again at higher fields. In addition, for B smaller than BSF we observe a resonance mode assigned to excitations due to Dzyaloshinskii-Moriya (DM)-interactions, thereby evidencing sizable DM interaction of approx 150 micro eV in LiFePO4. Both the magnetisation and the excitations up to high magnetic fields are described in terms of a mean-field theory model which extends recent zero field inelastic neutron scattering results. Our results imply that magnetic interactions as well as magnetic anisotropy have a sizable quadratic field dependence which we attribute to significant magnetostriction.

cond-mat.str-el↗

arXiv2020

Antisite disorder in the battery material LiFePO$_4$

We report detailed magnetometry and high-frequency electron spin resonance (HF-ESR) measurements which allow detailed investigation on Li-Fe antisite disorder in single-crystalline LiFePO$_4$, i.e., exchange of Fe$^{2+}$- and Li$^+$-ions. The data imply that magnetic moments of Fe$^{2+}$-ions at Li-positions do not participate in long-range antiferromagnetic order in LiFePO$_4$ but form quasi-free moments. Anisotropy axes of the magnetic moments at antisite defects are attached to the main crystallographic directions. The local character of these moments is confirmed by associated linear resonance branches detected by HF-ESR studies. Magnetic anisotropy shows up in significant zero-field splittings of $\Delta = 220(3)$~GHz, $\Delta'\sim50$~GHz and a highly anisotropic $g$-factor, i.e., $g_\mathrm{a} = 1.4$, $g_\mathrm{b} = 2.0$, and $g_\mathrm{c} = 6.3$. We demonstrate a general method to precisely determine Fe-antisite disorder in LiFePO$_4$ from magnetic studies which implies a density of paramagnetic Fe$^{2+}$-ions at Li-positions of 0.53\%.

cond-mat.mtrl-sci↗

arXiv2019

High-magnetic field phase diagram and failure of magnetic Gr\"uneisen scaling in LiFePO$_4$

We report the magnetic phase diagram of single-crystalline LiFePO$_4$ in magnetic fields up to 58~T and present a detailed study of magneto-elastic coupling by means of high-resolution capacitance dilatometry. Large anomalies at \tn\ in the thermal expansion coefficient $\alpha$ imply pronounced magneto-elastic coupling. Quantitative analysis yields the magnetic Gr\"uneisen parameter $\gamma_{\rm mag}=6.7(5)\cdot 10^{-7}$~mol/J. The positive hydrostatic pressure dependence $dT_{\rm N}/dp = 1.46(11)$~K/GPa is dominated by uniaxial effects along the $a$-axis. Failure of Gr\"uneisen scaling below $\approx 40$~K, i.e., below the peak temperature in the magneto-electric coupling coefficient [\onlinecite{toft2015anomalous}], implies several competing degrees of freedom and indicates relevance of recently observed hybrid excitations~[\onlinecite{yiu2017hybrid}]. A broad and strongly magnetic-field-dependent anomaly in $\alpha$ in this temperature regime highlight the relevance of structure changes. Upon application of magnetic fields $B||b$-axis, a pronounced jump in the magnetisation implies spin-reorientation at $B_{\rm SF} = 32$~T as well as a precursing phase at 29~T and $T=1.5$~K. In a two-sublattice mean-field model, the saturation field $B_{\rm sat,b} = 64(2)$~T enables the determination of the effective antiferromagnetic exchange interaction $J_{\rm af} = 2.68(5)$~meV as well as the anisotropies $D_{\rm b} = -0.53(4)$~meV and $D_{\rm c} = 0.44(8)$~meV.

cond-mat.str-el↗

arXiv2019

High-frequency EPR study on Cu$_4$Cu- and Co$_4$Co-metallacrown complexes

High-frequency/high-field electron paramagnetic resonance studies on two homo-nuclear 12-MC-4 metallacrown complexes Cu$_4$Cu and Co$_4$Co are presented. For Cu$_4$Cu, our data imply axial-type $g$-anisotropy with $g_{x}$ = 2.03 $\pm$ 0.01, $g_{y}$ = 2.04 $\pm$ 0.01, and $g_{z}$ = 2.23 $\pm$ 0.01, yielding $g=2.10 \pm 0.02$. No significant zero field splitting (ZFS) of the ground state mode is observed. In Co$_4$Co, we find a m$_S$ = $\pm$3/2 ground state with $g=2.66$. The data suggest large anisotropy $D$ of negative sign.

cond-mat.mes-hall↗

arXiv2019

The decisive role of magnetic anisotropy in honeycomb layered Li$_3$Ni$_2$SbO$_6$ and Na$_3$Ni$_2$SbO$_6$

The decisive role of magnetic anisotropy even in systems with small anisotropy is illustrated for the honeycomb-layered antiferromagnets The decisive role of magnetic anisotropy in honeycomb layered Li$_3$Ni$_2$SbO$_6$ and Na$_3$Ni$_2$SbO$_6$ with $A$ = Li and Na. Both systems evolve long range magnetic order below $T_{\rm N}$ = 14 and 16.5~K, respectively. The magnetic phase diagrams obtained from static magnetisation studies up to 15~T imply competing antiferromagnetic phases and a tricritical point at $T_{\rm N}$. The phase boundaries are visible in the dynamic response of the antiferromagnetic resonance modes, too, which investigation by means of high frequency/high field electron spin resonance enables precise determination of magnetic anisotropy. The anisotropy gap amounts to $\Delta = 360 \pm 2$~GHz in Na$_3$Ni$_2$SbO$_6$ while in Li$_3$Ni$_2$SbO$_6$ orthorhombicity is associated with $\Delta = 198 \pm 4$ and $218 \pm 4$~GHz. Above $T_{\rm N}$, the data imply short-range antiferromagnetic order up to at least 80~K. The data suggest a crucial role of anisotropy for selecting the actual spin structure at $B=0$~T.

cond-mat.str-el↗

arXiv2018

Magnetism and the phase diagram of MnSb$_2$O$_6$

Static and dynamic magnetic properties of P\={3}1$m$-phase MnSb$_2$O$_6$ have been studied by means of muon spin relaxation ($\mu$SR), high-frequency electron spin resonance (HF-ESR), specific heat, and magnetisation studies in magnetic fields up to 25\,T. The data imply onset of long-range antiferromagnetic order at $T_N$ =~8~K and a spin-flop-like transition at $B_{SF}\approx 0.7 - 1$~T. Below $T_N$, muon asymmetry exhibits well-defined oscillations indicating a narrow distribution of the local fields. A competing antiferromagnetic phase appearing below $T_2$ =~5.3~K is evidenced by a step in the magnetisation and a slight kink of the relaxation rate. Above $T_N$ , both $\mu$SR and HF-ESR data suggest short-range spin order. HF-ESR data show that local magnetic fields persist up to at least $12\cdot T_{\rm N}\approx 100$\,K. Analysis of the antiferromagnetic resonance modes and the thermodynamic spin-flop field suggest zero-field splitting of $\Delta \approx 18$\,GHz which implies small but finite magnetic anisotropy.

cond-mat.str-el↗

arXiv2018

Magnetoelastic coupling and ferromagnetic-type in-gap spin excitations in multiferroic $\alpha$-Cu$_2$V$_2$O$_7$

We investigate magnetoelectric coupling and low-energy magnetic excitations in multiferroic $\alpha$-Cu$_2$V$_2$O$_7$ by detailed thermal expansion, magnetostriction, specific heat and magnetization measurements in magnetic fields up to 15~T and by high-field/high-frequency electron spin resonance studies. Our data show negative thermal expansion in the temperature range $\leq 200$~K under study. Well-developed anomalies associated with the onset of multiferroic order (canted antiferromagnetism with a significant magnetic moment and ferroelectricity) imply pronounced coupling to the structure. We detect anomalous entropy changes in the temperature regime up to $\sim 80$~K which significantly exceed the spin entropy. Failure of Gr\"uneisen scaling further confirms that several dominant ordering phenomena are concomitantly driving the multiferroic order. By applying external magnetic fields, anomalies in the thermal expansion and in the magnetization are separated. Noteworthy, the data clearly imply the development of a canted magnetic moment at temperatures above the structural anomaly. Low-field magnetostriction supports the scenario of exchange-striction driven multiferroicity. We observe low-energy magnetic excitations well below the antiferromagnetic gap, i.e., a ferromagnetic-type resonance branch associated with the canted magnetic moment arising from Dzyaloshinsii-Moriya interactions. The anisotropy parameter $\tilde{D}=1.6(1)$~meV indicates a sizeable ratio of DM- and isotropic magnetic exchange.

cond-mat.str-el↗

arXiv2017

Electronic structure and magnetic properties of the strong-rung spin-1 ladder compound Rb$_3$Ni$_2$(NO$_3$)$_7$

Small single crystals of Rb$_3$Ni$_2$(NO$_3$)$_7$ were obtained by crystallization from anhydrous nitric acid solution of rubidium nitrate and nickel nitrate hexahydrate. The basic elements of the crystal structure of this new compound are isolated spin-1 two-leg ladders of Ni$^{2+}$-ions connected by (NO$_3$)$^-$ groups. The experimental data show the absence of long range magnetic order at T $\geq 2$~K. LDA+U calculations and the detailed analysis of the experimental data, i.e. of the magnetic susceptibility, the specific heat in magnetic fields up to 9~T, the magnetization, and of the high-frequency electron spin resonance data, enable quantitative estimates of the relevant parameters of the $S=1$ ladders in Rb$_3$Ni$_2$(NO$_3$)$_7$ . The rung-coupling $J_1 = 10.5$~K, the leg-coupling $J_2=1.6$~K, and the uniaxial anisotropy $|A| = 179$~GHz are obtained. The scenario of spin liquid quantum ground state is further corroborated by quantum Monte Carlo simulations of the magnetic susceptibility.

cond-mat.mtrl-sci↗

arXiv2016

Magnetic anisotropy and the phase diagram of chiral MnSb2O6

The magnetic phase diagram and low-energy magnon excitations of structurally and magnetically chiral MnSb2O6 are reported. The specific heat and the static magnetization are investigated in magnetic fields up to 9 and 30 T, respectively, while the dynamicmagnetic properties are probed by X-band as well as tunable high-frequency electron spin-resonance spectroscopy. Below TN = 11.5 K, we observe antiferromagnetic resonance modes which imply small but finite planar anisotropy showing up in a zero-field splitting of 20 GHz. The data are well described by means of an easy-plane two-sublattice model with the anisotropy field BA = 0.02 T. The exchange field BE = 13 T is obtained from the saturation field derived from the pulsed-field magnetization. A crucial role of the small anisotropy for the spin structure is reflected by competing antiferromagnetic phases appearing, at T = 2 K, in small magnetic fields at BC1 $\approx$ 0.5 T and BC2 = 0.9 T. We discuss the results in terms of spin reorientation and of small magnetic fields favoring helical spin structure over the cycloidal ground state which, at B = 0, is stabilized by the planar anisotropy. Above TN, short-range magnetic correlations up to >=60 K and magnetic entropy changes well above TN reflect the frustrated triangular arrangement of Mn2+ ions in MnSb2O6.

cond-mat.str-el↗

arXiv2014

Unusual spin fluctuations and magnetic frustration in olivine and non-olivine LiCoPO$_4$ detected by $^{31}$P and $^7$Li nuclear magnetic resonance

We report $^{31}$P and $^{7}$Li nuclear magnetic resonance (NMR) studies in new non-olivine LiZnPO$_4$-type LiCoPO$_4^\text{tetra}$ microcrystals, where the Co$^{2+}$ ions are tetrahedrally coordinated. Olivine LiCoPO$_4$, which was directly transformed from LiCoPO$_4^\text{tetra}$ by an annealing process, was also studied and compared. The uniform bulk magnetic susceptibility and the $^{31}$P Knight shift obey the Curie-Weiss law for both materials with a high spin Co$^{2+}$ ($3d^7$, $S=3/2$), but the Weiss temperature $Θ$ and the effective magnetic moment $μ_\text{eff}$ are considerably smaller in LiCoPO$_4^\text{tetra}$. The spin-lattice relaxation rate $T_1^{-1}$ reveals a quite different nature of the spin dynamics in the paramagnetic state of both materials. Our NMR results imply that strong geometrical spin frustration occurs in tetrahedrally coordinated LiCoPO$_4$, which may lead to the incommensurate magnetic ordering.

cond-mat.str-el↗

arXiv2009

Crystal lattice desolvation effects on the magnetic quantum tunneling of single-molecule magnets

High-frequency electron paramagnetic resonance (HFEPR) and AC susceptibility measurements are reported for a new high-symmetry Mn12 complex, [Mn12O12(O2CCH3)16(CH3OH)4].CH3OH. The results are compared with those of other high-symmetry spin S = 10 Mn12 single-molecule magnets (SMMs), including the original acetate, [Mn12(O2CCH3)16(H2O)4].2CH3CO2H.4H2O, and the [Mn12O12(O2CCH2Br)16(H2O)4].4CH2Cl2 & [Mn12O12(O2CCH2But)16(CH3OH)4].CH3OH complexes. These comparisons reveal important insights into the factors that influence the values of the effective barrier to magnetization reversal, Ueff, deduced on the basis of AC susceptibility measurements. In particular, we find that variations in Ueff can be correlated with the degree of disorder in a crystal which can be controlled by desolvating (drying) samples. This highlights the importance of careful sample handling when making measurements on SMM crystals containing volatile lattice solvents. The HFEPR data additionally provide important spectroscopic evidence suggesting that the relatively weak disorder induced by desolvation strongly influences the quantum tunneling interactions, and that it is under-barrier tunneling that is responsible for a consistent reduction in Ueff that is found upon drying samples. Meanwhile, the axial anisotropy deduced from HFEPR is found to be virtually identical for all four Mn12 complexes, with essentially no measurable reduction upon desolvation.

cond-mat.mes-hall↗

arXiv2009

Manifestation of Spin Selection Rules on the Quantum Tunneling of Magnetization in a Single Molecule Magnet

We present low temperature magnetometry measurements on a new Mn3 single-molecule magnet (SMM) in which the quantum tunneling of magnetization (QTM) displays clear evidence for quantum mechanical selection rules. A QTM resonance appearing only at elevated temperatures demonstrates tunneling between excited states with spin projections differing by a multiple of three: this is dictated by the C3 symmetry of the molecule, which forbids pure tunneling from the lowest metastable state. Resonances forbidden by the molecular symmetry are explained by correctly orienting the Jahn-Teller axes of the individual manganese ions, and by including transverse dipolar fields. These factors are likely to be important for QTM in all SMMs.

cond-mat.mes-hall↗