Anisotropy Energy Barrier Research Articles

Bioinspired directional structures for inhibiting wetting on super-melt-philic surfaces above 1200 °C

Over the past two decades, superhydrophobic surfaces that are easily created have aroused considerable attention for their superior performances in various applications at room temperature. Nowadays, there is a growing demand in special fields for the development of surfaces that can resist wetting by high-temperature molten droplets (>1200 °C) using facile design and fabrication strategies. Herein, bioinspired directional structures (BDSs) were prepared on Y2O3-stabilized ZrO2 (YSZ) surfaces using femtosecond laser ablation. Benefiting from the anisotropic energy barriers, the BDSs featured with no additional modifiers showed a remarkable increase from 9.2° to 60° in the contact angle of CaO–MgO–Al2O3–SiO2 (CMAS) melt and a 70.1% reduction in the spreading area of CMAS at 1250 °C, compared with polished super-CMAS-melt-philic YSZ surfaces. Moreover, the BDSs demonstrated exceptional wetting inhibition even at 1 400 °C, with an increase from 3.3° to 31.3° in contact angle and a 67.9% decrease in spreading area. This work provides valuable insight and a facile preparation strategy for effectively inhibiting the wetting of molten droplets on super-melt-philic surfaces at extremely high temperatures.

Superparamagnetic properties of metal-free nitrogen-doped graphene quantum dots

This article reports the superparamagnetic behavior of metal-free nitrogen-doped graphene quantum dots (N-GQDs). The pulsed laser ablation (PLA) method was utilized to synthesize N-GQDs with an average diameter of 3.45 nm and a high doping level (N/C) of 1.4. Magnetic properties of as-synthesized N-GQDs were explored by performing magnetization vs magnetic field (M–H) and magnetization vs temperature (M–T) measurements. M–H plots measured in a temperature range of 2–300 K revealed the superparamagnetic behavior of N-GQDs. The value of saturation magnetization was found to be directly correlated to nitrogen concentration and a saturation magnetization up to 28.7 emu/g was obtained at room temperature (300 K). M–T measurements with zero-field-cooled (ZFC) and field-cooled (FC) conditions were employed to study anisotropy energy barriers and blocking temperature. A variation in the blocking temperature (TB) from 288 to 61 K was observed when the external magnetic field (H) was changed from 0.1 to 0.6 T. The origin of superparamagnetism was attributed to the presence of graphitic nitrogen bonding configuration and defect states. The observed superparamagnetic properties along with the optical properties of N-GQDs create an opportunity for developing materials for biomedical applications and data recording devices.

Tailoring single-ion magnet properties of coordination polymer C11H18DyN3O9 (Dy-CP) using the radial effective charge model (RECM) and superposition model (SPM).

We investigate Dy-based coordination polymer C11H18DyN3O9 (Dy-CP) exhibiting single-ion magnet (SIM) properties, e.g., quantum tunnelling of magnetization (QTM), magnetic anisotropy, magnetic relaxation, and effective energy barrier (Ueff). To elucidate the underlying mechanisms, crystal field parameters (CFPs) for Dy3+ ions were modelled using the radial effective charge model (RECM) and superposition model (SPM), and the computational packages SIMPRE and SPECTRE. The modelled CFPs enable the prediction of the energy levels and associated wave functions, which successfully explain the field-induced Dy-CP SIM properties. The so-calculated magnetic susceptibility and isothermal magnetization match the experimental data reasonably well. The smaller energy separations of the first (Δ0-1 ∼ 31 cm-1) and the second (Δ0-2 = 74 cm-1) excited Kramers doublets suggest small Ueff = 65 cm-1 for Dy-CP. The magnetic moments of Dy3+ ions exhibit an easy-axis type magnetic anisotropy in the ground state, but change orientation in the excited states due to mixing of states from different Kramers doublets. Low-symmetry CF components play a crucial role in connecting different |±MJ〉 states within the ground multiplet, resulting in QTM and magnetic relaxation to the ground state occurring via the excited states. The RECM and SPM calculated CFP sets are standardized employing the 3DD package to enable meaningful comparison and assessing their mutual equivalence. The results demonstrate the correlation between structural and electronic features of the molecule and site symmetry and distortion of the local coordination polyhedra with SIM properties, offering insights for rational design of new SIMs. The importance of considering low-symmetry aspects in CFP modelling for accurate predictions of magnetic properties is highlighted. This study provides deeper understanding of field-induced behaviour in rare-earth-based SIMs and approaches for rationalization of experimentally measured SIMs' properties.

Interplay of Anisotropy Energy Barrier and Self-Heating Efficiency of Cobalt-Substituted CuFe2O4 Nanoparticles.

In this study, we delve into the intricate interplay between the anisotropy energy barrier and the self-heating efficiency of magnetic nanoparticles (MNPs). We embarked on this exploration by synthesizing Cu1-xCoxFe2O4 (x = 0, 0.1, 0.3, and 0.5) MNPs using a straightforward coprecipitation method. Our magnetic assessments, conducted at different temperatures, unveiled a notable trend as we traversed from x = 0.1 to x = 0.5. Specifically, we observed a consistent increase in saturation magnetization, coercivity, and remanence. This pattern also extended to the anisotropy energy barrier, which was derived from the effective anisotropy constant determined through the temperature dependency of the coercivity method. However, an intriguing twist emerged when we scrutinized the specific absorption rate (SAR), calculated via the Box-Lucas method. Contrary to much of the existing literature, our experimental results showcased a decline in SAR concerning x. This experimental work challenges the conventional understanding of the relationship between the anisotropy energy barrier and the SAR value of these nanoparticles. This study prompts us to reconsider the intricate mechanisms governing the relaxation of magnetic moments and subsequent heat release when subjected to an alternating magnetic field. By doing so, we aim to gain fresh insights into the self-heating properties of MNPs and optimize their utilization to better understand their heat-release properties and ensure that they are used as efficiently as possible in a variety of biomedical applications.

Modification in Magnetic Properties of CoFe2O4 Ferrite Nanoparticles Induced by 100MeV O+7 Ion Irradiation

In this work CoFe2O4 ferrite nanoparticles were prepared via sol-gel method using citric acid as chelating agent. The prepared nanoparticles was sintered at 700°C and the crystallite size is found 34 nm. In this investigation the effect of irradiation of 100 MeV O+7 beam on these nanoparticles with two fluences 5×1012 and 5×1013 ions/cm2 are studied. After irradiation the crystallite size is found to be reduced which is confirmed by transmission electron micrograph. The retentivity and coercivity changes with a measurable value while the saturation magnetization reduces slightly. The value of remanent magnetization increased from 30 emu/g to 34.6 emu/g, it can be attributed to increase of magnetic hardness. The increase in squareness ratio after irradiation leads to increase in anisotropic energy barrier of CoFe2O4 ferrite nanoparticles. Anisotropy field about doubles after irradiation and corresponding anisotropy constant also doubles with the used fluences.

Direct observation of the magnetic anisotropy of an Fe(II) spin crossover molecular thin film

In this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H2B(pz)2)2(bipy)] (pz = pyrazol−1−yl, bipy = 2,2′−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10−5 eV molecule−1 indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule−1, respectively. Furthermore, the estimated g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations.

Tuning Crystal Packing and Magnetic Properties in a Series of [Dy12] Metallocubanes Based on Azobenzene Derivatives of Salicylic Acid.

A series of four new Dy12 dodecanuclear clusters based on azobenzene derivative ligands of salicylic acid (L1-L4) has been synthesized and characterized in the crystalline phase using X-ray diffraction on single crystal and powder, IR spectroscopy, elemental analysis, and DSC-TGA methods. It was revealed that all obtained clusters exhibit the formation of the similar metallic cluster nodes, as vertex-sharing heterocubanes, obtained from four Dy3+ cations, three bridging hydroxyl groups, and O atoms from the salicylic ligands. The coordination geometry around the Dy(III) centers has been carefully analyzed. Whereas Dy12-L1 and Dy12-L2 with L1 and L2 containing Me and OMe groups in para positions of the phenyl rings, respectively, form similar porous 3D diamond-like molecular networks due to CH-π interactions, for Dy12-L3 with L3 bearing NO2-electron-withdrawing group, the generation of 2D molecular grids assembled by π-π staking is observed, and for Dy12-L4 with L4 bearing phenyl substituent, 3D hexagonal channels have been generated. The complexes Dy12-L1, Dy12-L2, and Dy12-L3 exhibit a zero-field slow magnetic relaxation effect. After UV irradiation of Dy12-L1, a decrease of the magnetic anisotropy energy barrier displaying the possibility of control over magnetic properties by the external stimulus has been observed.

Random magnetic anisotropy driven transitions in the layered perovskite LaSrCoO4

Attempts to unravel the nature of magnetic ordering in LaSrCoO$_4$ (Co$^{3+}$), a compound intermediate between antiferromagnetic (AFM) La$_2$CoO$_4$ (Co$^{2+}$) and ferromagnetic (FM) Sr$_2$CoO$_4$ (Co$^{4+}$), have met with a limited success so far. In this report, the results of a thorough investigation of dc magnetization and ac susceptibility (ACS) in single-phase LaSrCoO$_4$ provide clinching evidence for a thermodynamic paramagnetic (PM) - ferromagnetic (FM) phase transition at T$_{c}$ = 220.5 K, followed at lower temperature (T$_{g}$ = 7.7 K) by a transition to the cluster spin glass (CSG) state. Analysis of the low-field Arrott plot isotherms, in the critical region near T$_{c}$, in terms of the Aharony-Pytte scaling equation of state clearly establishes that the PM-FM transition is basically driven by random magnetic anisotropy (RMA). For temperatures below $\approx$ 30 K, large enough RMA destroys long-range FM order by breaking up the infinite FM network into FM clusters of finite size and leads to the formation of a CSG state at temperatures T $\lesssim$ 8 K by promoting freezing of finite FM clusters in random orientations. Increasing strength of the single-ion magnetocrystalline anisotropy (and hence RMA) with decreasing temperature is taken to reflect an increase in the number of low-spin (LS) Co$^{3+}$ ions at the expense of that of high-spin (HS) Co$^{3+}$ ions. At intermediate temperatures (30 K $\lesssim T \lesssim$ 180 K), spin dynamics has contributions from the infinite FM network (fast relaxation governed by a single anisotropy energy barrier) and finite FM clusters (extremely slow stretched exponential relaxation due to hierarchical energy barriers).

Slow Magnetic Relaxation and Luminescence Properties in Tetra β-Diketonate Lanthanide(III) Complexes

The reaction of [Ln(btfa)3(H2O)2] (btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate) with additional 4,4,4-trifluoro-1-phenyl-1,3-butanedione (Hbtfa) and acridine (Acr) in ethanol allows the isolation of the mononuclear compounds HAcr[Nd(btfa)4]·EtOH, (1) and HAcr[Ln(btfa)4], Ln = Dy (2) and Yb (3); HAcr+ = acridinium cation. Magnetic measurements indicate that complexes 1–3 show field-induced single-ion magnet behavior with anisotropy energy barriers and preexponential factors of Ueff = 20.7 cm−1, τ0 = 24.5 × 10−8 s; Ueff = 40.5 cm−1, τ0 = 8.6 × 10−10 s and Ueff = 22.7 cm−1, τ0 = 8.4 × 10−8 s, for 1–3 respectively. The solid-state luminescence emission in the NIR region shows efficient energy transfer from the 4,4,4-trifluoro-1-phenyl-1,3-butanedionate ligands to the central Ln3+ ion in the case of compounds 1 and 3.

Helimagnet-based nonvolatile multi-bit memory units

In this Letter, we present a design of a helimagnet-based emerging memory device that is capable of storing multiple bits of information per device. The device consists of a helimagnet layer placed between two ferromagnetic layers, which allows us to lock-in specific spin configurations. The bottom pinned layer has high anisotropy energy or stays exchange biased, which keeps its spin configuration fixed on a specific direction, while the top layer is free to rotate under the influence of in-plane magnetic fields. We begin by finding the relaxed spin structure, which is the result of the competition between the Dzyaloshinskii–Moriya interaction (DMI) and exchange energy and is referred to as the equilibrium state (“0”). The writing of a memory state is simulated by applying an in-plane field that rotates and transforms the spin configurations of the memory device. Our results indicate that stable configurations can be achieved at rotations of an integer multiple of 180° (corresponding to states “−2,” “−1,” “1,” “2,” etc.), where the anisotropy stabilizes the free layer and, thus, the exchange coupled helimagnet. These states are separated by magnetic energy barriers and intermediate, unstable spin configurations tend to revert to their adjacent states. By simply changing the direction of the field, we can achieve multi-bit data storage per unit memory cell. The maximum number of bits is reached when the anisotropy energy barriers cannot withstand the strong DMI energy. Reading can be done by evaluating the different resistance states due to the twisted spin texture.

Antiferromagnet thickness dependence and rotatable spins in exchange biased CoO/Fe films

The emergence of exchange bias and coercivity enhancement has been investigated in epitaxial CoO/Fe films with varied antiferromagnet (AF) thicknesses, even smaller than the critical value where the frozen CoO spins are detectable. Vector magnetometry and first-order reversal curve (FORC) measurements reveal different CoO thickness dependence of the exchange bias and coercivity enhancement, including the evolution of magnetization reversal from a high coercivity, low bias phase due to rotatable CoO moments to a high bias, low coercivity phase due to frozen CoO moments. The AF domain state is found to be metastable, which can be reoriented by external and exchange fields prior to the appearance of frozen spins, pointing to a generic origin of the training effect. Monte Carlo simulations show that the AF anisotropy energy barrier and the rotatable spins induced by magnetic field and exchange interaction at the interface are responsible for the observed effects.

Side-Group Effect on the Slow Relaxations of {Dy2} Single-Molecule Magnets with Confined N2O6 Donors.

Deep insights into and substantial enhancement of the effective anisotropy energy barrier for magnetization reversal (Ueff) are vitally important for the technological applications of dysprosium(III)-based single-molecule magnets (Dy-SMMs). To fully refine the ligand-field effect on spin relaxation, four centrosymmetric {Dy2} entities with formula [Dy2(CH3OH)2L2(RCOO)2] (H2L = 2-hydroxy-N'-((pyridin-2-yl)methylene)benzohydrazide) have been solvothermally prepared by varying the side groups of carboxylate coligands (RCOO-, R = CF3 for 1, H for 2, CH3 for 3, and Cp2Fe for 4). Structural analyses reveal that all of the DyIII carriers in 1-4 have the same N2O6 donor environments, and the non-coordinative R groups attached to the equatorial carboxylate bridges have not substantially changed the binding ability of the shortest Dy-Ophenolate bonds located at the axial position of the ligand field. Interestingly, the side groups have monotonically decreased the zero-field Ueff barriers of these weak antiferromagnetically coupled {Dy2} analogues from 721 K down to 379 K. Further electronic structure calculations demonstrate that the main magnetic axes of 1-4 are highly dominated by these comparable Dy-Ophenolate short bonds, and the g tensors have produced gradually increased transverse components responsible significantly for the decreased Ueff barriers. Additionally, thermally assisted relaxations occur preferably through the second (for 1) and the first (for 2-4) Kramer doublets. These interesting findings afford a new side-group effect to comprehensively understand the magnetostructural relationships and advance the rational design of high-performance Dy-SMMs.

Robust and Programmable Logic-In-Memory Devices Exploiting Skyrmion Confinement and Channeling Using Local Energy Barriers

Magnetic skyrmions are promising candidates for logic-in-memory applications, intrinsically merging high density non-volatile data storage with computing capabilities, owing to their nanoscale size, fast motion, and mutual repulsions. However, concepts proposed so far suffer from reliability issues as well as inefficient conversion of magnetic information to electrical signals. In this paper, we propose a logic-in-memory device which exploits skyrmion confinement and channeling using anisotropy energy barriers to achieve reliable data storage and synchronous shift in racetracks combined with cascadable and reprogrammable logics relying purely on magnetic interactions. The device combines a racetrack shift register based on skyrmions confined in nanodots with Full Adder (FA) gates. The designed FA is reprogrammable and cascadable and can also be used to perform simple logic operations such as AND, OR, NOT, NAND, XOR and NXOR. The monolithic design of the logic gate and the absence of any complex electrical contacts makes the device ideal for integration with conventional CMOS circuitry.

Programmable Skyrmion Logic Gates Based on Skyrmion Tunneling

Magnetic skyrmions are promising candidates as elementary nanoscale bits in logic-in-memory devices, intrinsically merging high density memory and computing capabilities. Here we exploit the dynamics of skyrmions interacting with anisotropy energy barriers patterned by ion irradiation to design programmable logic gates. Using micromagnetic simulations with experimental parameters, we show that a fine tuning of the barrier height and width allows the selective tunneling of skyrmions between parallel nanotracks triggered by skyrmion-skyrmion interaction. This can be leveraged to design skyrmion De-multiplexer (DMux) logic gate which works solely using skyrmions as logic inputs. By cascading and connecting demultiplexer gates with a specific topology, we develop a fully programmable logic gate capable of producing any possible logic output as a sum of all minterms generated by a given set of inputs without requiring any complex additional electric/magnetic interconversion. The proposed design is fully conservative and cascadable and paves a new pathway for full skyrmionic-based logic-in-memory devices.

Strain-engineered topological phase transitions in ferrovalley 2H−RuCl2 monolayer

Ferrovalley and topology are two basic concepts in both fundamental research fields and emerging device applications. So far, reports are extremely scarce regarding the coupling of these two scenarios in a single material system. By first-principles calculations and Monte Carlo simulations, we predict a highly stable intrinsic ferrovalley $2H\text{\ensuremath{-}}{\mathrm{RuCl}}_{\text{2}}$ semiconductor with an easy out-of-plane magnetization and a high Curie temperature of 260 K. Due to the combination of exchange interaction and spin-orbit coupling, the system exhibits a spontaneous valley polarization of 240 meV in the top valence band, which is further confirmed by a first-order perturbation theory. Moreover, its out-of-plane ferromagnetic ordering can remain rather robust and survive up to 547 K under $\ensuremath{-}5$% compressive strain well above room temperature. On the other hand, the application of tensile strain can drive the system from the ferrovalley phase into a half-valley-metal state with 100% spin and valley polarizations, followed then by a quantum anomalous Hall (QAH) phase in support of scarce high-temperature QAH effect. Beyond around 2% tensile strain, the system is switched to the in-plane magnetization. If the magnetization is steered to the out-of-plane direction through overcoming the magnetic anisotropy energy barriers, the system is further transitioned from the QAH phase to another half-valley-metal state with the rise of tensile strain, and finally restores to the initial ferrovalley phase. Once synthesized, monolayer $2H\text{\ensuremath{-}}{\mathrm{RuCl}}_{\text{2}}$ would find many important applications in spintronic, valleytronic, and topological electronic nanodevices.

Dependence of hysteresis loss of immobilized magnetic nanoparticles on the easy-axis angle: Effect of easy-axis alignment

Magnetic nanoparticles (MNPs) have been widely studied for hyperthermia applications. We studied the hysteresis loss of immobilized MNPs with partially aligned easy axes. For this purpose, we investigated how the AC magnetization (M–H) curve of MNP depended on the easy-axis angle of magnetization, β, via numerical simulations of the Fokker–Planck equation. We clarified the dependences of the coercive field, Hc, and the hysteresis loss, A, on β. We, thus, obtained analytical expressions for Hc(β) and A(β) that explain simulation results for a wide range of MNP parameters and excitation conditions. The angle dependences were also discussed on the basis of magnetic moment reversal over the anisotropy energy barrier. We then examined the hysteresis loss of an MNP sample with partial alignment of the easy axes and obtained an expression for the loss by combining A(β) and a distribution function for β. We quantitatively clarified the relationship between the loss and the degree of easy-axis alignment. The loss of immobilized MNPs can be increased by a factor of 2.2 by using easy-axis alignment relative to the case of randomly oriented easy axes. Finally, we examined the alignment of easy axes induced by an AC field in suspended MNPs and showed that the loss of immobilized MNPs with partially aligned easy axes can be used to estimate the loss for suspended MNPs.

Deciphering the Role of Anions and Secondary Coordination Sphere in Tuning Anisotropy in Dy(III) Air-Stable D5h SIMs.

Precise control of the crystal field and symmetry around the paramagnetic spin centre has recently facilitated the engineering of high-temperature single-ion magnets (SIMs), the smallest possible units for future spin-based devices. In the present work, we report a series of air-stable seven coordinate Dy(III) SIMs {[L2 Dy(H2 O)5 ][X]3 ⋅L2 ⋅n(H2 O), n = 0, X = Cl (1), n=1, X = Br (2), I (3)} possessing pseudo-D5h symmetry or pentagonal bipyramidal coordination geometry with high anisotropy energy barrier (Ueff ) and blocking temperature (TB ). While the strong axial coordination from the sterically encumbered phosphonamide, t BuPO(NHi Pr)2 (L), increases the overall anisotropy of the system, the presence of high symmetry significantly quenches quantum tunnelling of magnetization, which is the prominent deactivating factor encountered in SIMs. The energy barrier (Ueff ) and the blocking temperature (TB ) decrease in the order 3>2>1 with the change of anions from larger iodide to smaller strongly hydrogen-bonded chloride in the secondary coordination sphere, albeit the local coordination geometry and the symmetry around the Dy(III) display only slight deviations. Ab initio CASSCF/RASSI-SO/SINGLE_ANISO calculations provide deeper insights into the dynamics of magnetic relaxation in addition to the role of the secondary coordination sphere in modulating the anisotropy of the D5h systems, using diverse models. Thus, in addition to the importance of the crystal field and the symmetry to obtain high-temperature SIMs, this study also probes the significance of the secondary coordination sphere that can be tailored to accomplish novel SIMs.

Switching the Local Symmetry from D5h to D4h for Single-Molecule Magnets by Non-Coordinating Solvents

A solvent effect towards the performance of two single-molecule magnets (SMMs) was observed. The tetrahydrofuran and toluene solvents can switch the equatorial coordinated 4-Phenylpyridine (4-PhPy) molecules from five to four, respectively, in [Dy(OtBu)2(4-PhPy)5]BPh41 and Na{[Dy(OtBu)2(4-PhPy)4][BPh4]2}∙2thf∙hex 2. This alternation significantly changes the local coordination symmetry of the Dy(III) center from D5h to D4h for 1 and 2, seperately. Magnetic studies show that the magnetic anisotropy energy barrier of 2 is higher than that of 1, while the relation of blocking temperature is just on the contrary due to the symmetry effect. The calculations of the electrostatic potential successfully explained the driving force of solvents for the molecular structure change, confirming the feasibility of adjusting the performance of SMMs via diverse solvents.

Effect of Grinding and the Mill Type on Magnetic Properties of Carboxylated Multiwall Carbon Nanotubes.

The influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties.

Equation-of-Motion Coupled-Cluster Protocol for Calculating Magnetic Properties: Theory and Applications to Single-Molecule Magnets.

We present a new computational protocol for computing macroscopic magnetic properties of transition-metal complexes using the equation-of-motion coupled-cluster (EOM-CC) framework. The approach follows a two-step state-interaction scheme: we first compute zero-order states using nonrelativistic EOM-CC and then use these states to evaluate matrix elements of the spin-orbit and Zeeman operators. Diagonalization of the resulting Hamiltonian yields spin-orbit- and field-perturbed eigenstates. Temperature- and field-dependent magnetization and susceptibility are computed by numerical differentiation of the partition function. To compare with powder-sample experiments, these quantities are numerically averaged over field orientations. We applied this protocol to several single-molecule magnets (SMMs) with Fe(II) and Fe(III) in trigonal pyramidal, linear, and trigonal bipyramidal coordination environments. We described the underlying electronic structure by the electron-attachment (EOM-EA) and spin-flip (EOM-SF) variants of EOM-CC. The computed energy barriers for spin inversion, and macroscopic magnetization and susceptibility agree well with experimental data. Trends in magnetic anisotropy and spin-reversal energy barriers are explained in terms of a molecular orbital picture rigorously distilled from spinless transition density matrices between many-body states. The results illustrate excellent performances of EOM-CC in describing magnetic behavior of mononuclear transition-metal SMMs.