Magnetic Exchange Interactions in Binuclear and Tetranuclear Iron (III) Complexes Described by Spin-Flip DFT and Heisenberg Effective Hamiltonians

Low-energy spectra of single-molecule magnets (SMMs) are often described by the Heisenberg Hamiltonian. Within this formalism, exchange interactions between magnetic centers determine the ground-state multiplicity and energy separation between the ground and excited states. In this contribution, we extract exchange coupling constants (J) for a set of iron (III) binuclear and tetranuclear complexes from all-electron calculations using non-collinear spin-flip time-dependent density functional theory (NC-SF-TDDFT). For the series of binuclear complexes with J-values ranging from -6 to -132 cm−1 , our benchmark calculations using the short-range hybrid LRC-ωPBEh functional and 6-31G(d,p) basis set agree well (mean absolute error of 4.7 cm−1) with the experimentally derived values. For the tetranuclear SMMs, the computed J constants are within 6 cm−1 from the values extracted from the experiment. We explore the range of applicability of the Heisenberg model by analyzing the radical character in the binuclear iron (III) complexes using natural orbitals (NO) and their occupations. On the basis of the number of effectively unpaired electrons and the NO occupancies, we attribute larger errors observed in strongly anti-ferromagnetic species to an increased ionic character. The results illustrate the efficiency of the spin-flip protocol for computing the exchange couplings and the utility of the NO analysis in assessing the validity of effective spin Hamiltonians.

Magnetic Exchange Interactions in Binuclear and Tetranuclear Iron (III) Complexes Described by Spin-Flip DFT and Heisenberg Effective Hamiltonians

Low-energy spectra of single-molecule magnets (SMMs) are often described by the Heisenberg Hamiltonian. Within this formalism, exchange interactions between magnetic centers determine the ground-state multiplicity and energy separation between the ground and excited states. In this contribution, we extract exchange coupling constants (J) for a set of iron (III) binuclear and tetranuclear complexes from all-electron calculations using non-collinear spin-flip time-dependent density functional theory (NC-SF-TDDFT). For the series of binuclear complexes with J-values ranging from -6 to -132 cm−1 , our benchmark calculations using the short-range hybrid LRC-ωPBEh functional and 6-31G(d,p) basis set agree well (mean absolute error of 4.7 cm−1) with the experimentally derived values. For the tetranuclear SMMs, the computed J constants are within 6 cm−1 from the values extracted from the experiment. We explore the range of applicability of the Heisenberg model by analyzing the radical character in the binuclear iron (III) complexes using natural orbitals (NO) and their occupations. On the basis of the number of effectively unpaired electrons and the NO occupancies, we attribute larger errors observed in strongly anti-ferromagnetic species to an increased ionic character. The results illustrate the efficiency of the spin-flip protocol for computing the exchange couplings and the utility of the NO analysis in assessing the validity of effective spin Hamiltonians.

Spin-dependent vibronic response of a carbon radical ion in two-dimensional WS2

Atomic spin centers in 2D materials are a highly anticipated building block for quantum technologies. Here, we demonstrate the creation of an effective spin-1/2 system via the atomically controlled generation of magnetic carbon radical ions (CRIs) in synthetic two-dimensional transition metal dichalcogenides. Hydrogenated carbon impurities located at chalcogen sites introduced by chemical doping are activated with atomic precision by hydrogen depassivation using a scanning probe tip. In its anionic state, the carbon impurity is computed to have a magnetic moment of 1 μB resulting from an unpaired electron populating a spin-polarized in-gap orbital. We show that the CRI defect states couple to a small number of local vibrational modes. The vibronic coupling strength critically depends on the spin state and differs for monolayer and bilayer WS2. The carbon radical ion is a surface-bound atomic defect that can be selectively introduced, features a well-understood vibronic spectrum, and is charge state controlled.

Field-induced quantum spin disordered state in spin-1/2 honeycomb magnet Na2Co2TeO6

Spin-orbit coupled honeycomb magnets with the Kitaev interaction have received a lot of attention due to their potential of hosting exotic quantum states including quantum spin liquids. Thus far, the most studied Kitaev systems are 4d/5d-based honeycomb magnets. Recent theoretical studies predicted that 3d-based honeycomb magnets, including Na2Co2TeO6 (NCTO), could also be a potential Kitaev system. Here, we have used a combination of heat capacity, magnetization, electron spin resonance measurements alongside inelastic neutron scattering (INS) to study NCTO’s quantum magnetism, and we have found a field-induced spin disordered state in an applied magnetic field range of 7.5 T < B (⊥ b-axis) < 10.5 T. The INS spectra were also simulated to tentatively extract the exchange interactions. As a 3d-magnet with a field-induced disordered state on an effective spin-1/2 honeycomb lattice, NCTO expands the Kitaev model to 3d compounds, promoting further interests on the spin-orbital effect in quantum magnets.

Voltage-dependent plasticity of spin-polarized conductance in phenyl-based single-molecule magnetic tunnel junctions

Synaptic strengths between neurons in brain networks are highly adaptive due to synaptic plasticity. Spike-timing-dependent plasticity (STDP) is a form of synaptic plasticity induced by temporal correlations between the firing activity of neurons. The development of experimental techniques in recent years enabled the realization of brain-inspired neuromorphic devices. Particularly, magnetic tunnel junctions (MTJs) provide a suitable means for the implementation of learning processes in molecular junctions. Here, we first considered a two-neuron motif subjected to STDP. By employing theoretical analysis and computer simulations we showed that the dynamics and emergent structure of the motif can be predicted by introducing an effective two-neuron synaptic conductance. Then, we considered a phenyl-based single-molecule MTJ connected to two ferromagnetic (FM) cobalt electrodes and investigated its electrical properties using the non-equilibrium Green’s function (NEGF) formalism. Similar to the two-neuron motif, we introduced an effective spin-polarized conductance in the MTJ. Depending on the polarity, frequency and strength of the bias voltage applied to the MTJ, the system can learn input signals by adaptive changes of the effective conductance. Interestingly, this voltage-dependent plasticity is an intrinsic property of the MTJ where its behavior is reminiscent of the classical temporally asymmetric STDP. Furthermore, the shape of voltage-dependent plasticity in the MTJ is determined by the molecule-electrode coupling strength or the length of the molecule. Our results may be relevant for the development of single-molecule devices that capture the adaptive properties of synapses in the brain.

Spin–orbit torque driven magnetization switching in W/CoFeB/MgO-based type-Y three terminal magnetic tunnel junctions

We have studied current induced magnetization switching in W/CoFeB/MgO based three terminal magnetic tunnel junctions. The switching driven by spin—orbit torque (SOT) is evaluated in the so-called type-Y structure, in which the magnetic easy-axis of the CoFeB layer lies in the film plane and is orthogonal to the current flow. The effective spin Hall angle estimated from the bias field dependence of critical current (Ic) is ~ 0.07. The field and current dependence of the switching probability are studied. The field and DC current induced switching can be described using a model based on thermally assisted magnetization switching. In contrast, the 50 ns long pulse current dependence of the switching probability shows significant deviation from the model, even if contribution from the field-like torque is included. The deviation is particularly evident when the threshold switching current is larger. These results show that conventional thermally assisted magnetization switching model cannot be used to describe SOT induced switching using short current pulses.