Showing papers on "Spin states published in 2016"

Field-induced conductance switching by charge-state alternation in organometallic single-molecule junctions

Abstract: Charge transport through single molecules can be influenced by the charge and spin states of redox-active metal centres placed in the transport pathway. These intrinsic properties are usually manipulated by varying the molecule's electrochemical and magnetic environment, a procedure that requires complex setups with multiple terminals. Here we show that oxidation and reduction of organometallic compounds containing either Fe, Ru or Mo centres can solely be triggered by the electric field applied to a two-terminal molecular junction. Whereas all compounds exhibit bias-dependent hysteresis, the Mo-containing compound additionally shows an abrupt voltage-induced conductance switching, yielding high-to-low current ratios exceeding 1,000 at bias voltages of less than 1.0 V. Density functional theory calculations identify a localized, redox-active molecular orbital that is weakly coupled to the electrodes and closely aligned with the Fermi energy of the leads because of the spin-polarized ground state unique to the Mo centre. This situation provides an additional slow and incoherent hopping channel for transport, triggering a transient charging effect in the entire molecule with a strong hysteresis and large high-to-low current ratios.

A quantum phase switch between a single solid-state spin and a photon

Abstract: Interactions between single spins and photons are essential for quantum networks and distributed quantum computation. Achieving spin-photon interactions in a solid-state device could enable compact chip-integrated quantum circuits operating at gigahertz bandwidths. Many theoretical works have suggested using spins embedded in nanophotonic structures to attain this high-speed interface. These proposals implement a quantum switch where the spin flips the state of the photon and a photon flips the spin state. However, such a switch has not yet been realized using a solid-state spin system. Here, we report an experimental realization of a spin-photon quantum switch using a single solid-state spin embedded in a nanophotonic cavity. We show that the spin state strongly modulates the polarization of a reflected photon, and a single reflected photon coherently rotates the spin state. These strong spin-photon interactions open up a promising direction for solid-state implementations of high-speed quantum networks and on-chip quantum information processors using nanophotonic devices.

Spin–orbit coupled molecular quantum magnetism realized in inorganic solid

Abstract: Molecular quantum magnetism involving an isolated spin state is of particular interest due to the characteristic quantum phenomena underlying spin qubits or molecular spintronics for quantum information devices, as demonstrated in magnetic metal-organic molecular systems, the so-called molecular magnets. Here we report the molecular quantum magnetism realized in an inorganic solid Ba3Yb2Zn5O11 with spin-orbit coupled pseudospin-½ Yb(3+) ions. The magnetization represents the magnetic quantum values of an isolated Yb4 tetrahedron with a total (pseudo)spin 0, 1 and 2. Inelastic neutron scattering results reveal that a large Dzyaloshinsky-Moriya interaction originating from strong spin-orbit coupling of Yb 4f is a key ingredient to explain magnetic excitations of the molecular magnet states. The Dzyaloshinsky-Moriya interaction allows a non-adiabatic quantum transition between avoided crossing energy levels, and also results in unexpected magnetic behaviours in conventional molecular magnets.

A Unified Treatment of the Relationship Between Ligand Substituents and Spin State in a Family of Iron(II) Complexes.

Abstract: The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)2]2+ (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature (Tinline image ) in solution vs. the relevant Hammett parameter show that the low-spin state of the complex is stabilized by electron-withdrawing pyridyl (“X”) substituents, but also by electron-donating pyrazolyl (“Y”) substituents. Moreover, when a subset of complexes with halogeno X or Y substituents is considered, the two sets of compounds instead show identical trends of a small reduction in Tinline image for increasing substituent electronegativity. DFT calculations reproduce these disparate trends, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe-L σ and π bonding.

Molecular-scale dynamics of light-induced spin cross-over in a two-dimensional layer.

Abstract: Spin cross-over molecules show the unique ability to switch between two spin states when submitted to external stimuli such as temperature, light or voltage. If controlled at the molecular scale, such switches would be of great interest for the development of genuine molecular devices in spintronics, sensing and for nanomechanics. Unfortunately, up to now, little is known on the behaviour of spin cross-over molecules organized in two dimensions and their ability to show cooperative transformation. Here we demonstrate that a combination of scanning tunnelling microscopy measurements and ab initio calculations allows discriminating unambiguously between both states by local vibrational spectroscopy. We also show that a single layer of spin cross-over molecules in contact with a metallic surface displays light-induced collective processes between two ordered mixed spin-state phases with two distinct timescale dynamics. These results open a way to molecular scale control of two-dimensional spin cross-over layers.

Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites

Abstract: Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength.

Spinning around in Transition-Metal Chemistry

Abstract: ConspectusThe great diversity and richness of transition metal chemistry, such as the features of an open d-shell, opened a way to numerous areas of scientific research and technological applications. Depending on the nature of the metal and its environment, there are often several energetically accessible spin states, and the progress in accurate theoretical treatment of this complicated phenomenon is presented in this Account.The spin state energetics of a transition metal complex can be predicted theoretically on the basis of density functional theory (DFT) or wave function based methodology, where DFT has advantages since it can be applied routinely to medium-to-large-sized molecules and spin-state consistent density functionals are now available. Additional factors such as the effect of the basis set, thermochemical contributions, solvation, relativity, and dispersion, have been investigated by many researchers, but challenges in unambiguous assignment of spin states still remain. The first DFT studi...

Hysteretic Four‐Step Spin Crossover within a Three‐Dimensional Porous Hofmann‐like Material

Abstract: Materials that display multiple stepped spin crossover (SCO) transitions with accompanying hysteresis present the opportunity for ternary, quaternary, and quinary electronic switching and data storage but are rare in existence. Herein, we present the first report of a four-step hysteretic SCO framework. Single-crystal structure analysis of a porous 3D Hofmann-like material showed long-range ordering of spin states: HS, HS0.67LS0.33, HS0.5LS0.5, HS0.33LS0.67, and LS. These detailed structural studies provide insight into how multistep SCO materials can be rationally designed through control of host–host and host–guest interactions.

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

Abstract: The relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal–ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N‒H groups consistently stabilizes the low-spin state, where this has been quantified.

Cumulant Approximated Second-Order Perturbation Theory Based on the Density Matrix Renormalization Group for Transition Metal Complexes: A Benchmark Study

Abstract: The complete active space second order perturbation theory (CASPT2) can be extended to larger active spaces by using the density matrix renormalization group (DMRG) as solver. Two variants are commonly used: the costly DMRG-CASPT2 with exact 4-particle reduced density matrix (4-RDM) and the cheaper DMRG-cu(4)-CASPT2 in which the 4-cumulant is discarded. To assess the accuracy and limitations of the latter variant DMRG-cu(4)-CASPT2 we study the spin state energetics of iron porphyrin Fe(P) and its model compound FeL2, a model for the active center of NiFe hydrogenase, and manganese-oxo porphyrin MnO(P)+; a series of excited states of chromium hexacarbonyl Cr(CO)6; and the interconversion of two Cu2O22+ isomers. Our results clearly show that PT2 on top of DMRG is essential in order to obtain quantitative results for transition metal complexes. Good results were obtained with DMRG-cu(4)-CASPT2 as compared to full CASPT2 and DMRG-CASPT2 in calculations with small- and medium-sized active spaces. In calculatio...

Stretching-Induced Conductance Increase in a Spin-Crossover Molecule.

Abstract: We investigate transport through mechanically triggered single-molecule switches that are based on the coordination sphere-dependent spin state of FeII-species. In these molecules, in certain junction configurations the relative arrangement of two terpyridine ligands within homoleptic FeII-complexes can be mechanically controlled. Mechanical pulling may thus distort the FeII coordination sphere and eventually modify their spin state. Using the movable nanoelectrodes in a mechanically controlled break-junction at low temperature, current–voltage measurements at cryogenic temperatures support the hypothesized switching mechanism based on the spin-crossover behavior. A large fraction of molecular junctions formed with the spin-crossover-active FeII-complex displays a conductance increase for increasing electrode separation and this increase can reach 1–2 orders of magnitude. Theoretical calculations predict a stretching-induced spin transition in the FeII-complex and a larger transmission for the high-spin c...

Current Switching Coupled to Molecular Spin-States in Large-Area Junctions.

Abstract: The fabrication of large-area vertical junctions with a molecular spin-crossover complex displaying concerted changes of spin degrees of freedom and charge-transport properties is reported. Fabricated devices allow spin-state switching in the spin-crossover layer to be triggered and probed by optical means, while detecting associated changes in electrical resistance in the junctions.

Spin-orbit-coupled two-electron Fermi gases of ytterbium atoms

Abstract: We demonstrate all-optical implementation of spin-orbit coupling (SOC) in a two-electron Fermi gas of $^{173}\mathrm{Yb}$ atoms by coupling two hyperfine ground states with a narrow optical transition. Due to the $\mathrm{SU}(N)$ symmetry of the $^{1}S_{0}$ ground-state manifold which is insensitive to external magnetic fields, an optical ac Stark effect is applied to split the ground spin states, which exhibits a high stability compared with experiments on alkali-metal and lanthanide atoms, and separate out an effective spin-$\frac{1}{2}$ subspace from other hyperfine levels for the realization of SOC. The dephasing spin dynamics when a momentum-dependent spin-orbit gap is suddenly opened and the asymmetric momentum distribution of the spin-orbit-coupled Fermi gas are observed as a hallmark of SOC. The realization of all-optical SOC for ytterbium fermions should offer a route to a long-lived spin-orbit-coupled Fermi gas and greatly expand our capability of studying spin-orbit physics with alkaline-earth-metal-like atoms.

Spin State as a Marker for the Structural Evolution of Nature's Water-Splitting Catalyst.

Abstract: In transition-metal complexes, the geometric structure is intimately connected with the spin state arising from magnetic coupling between the paramagnetic ions. The tetramanganese–calcium cofactor that catalyzes biological water oxidation in photosystem II cycles through five catalytic intermediates, each of which adopts a specific geometric and electronic structure and is thus characterized by a specific spin state. Here, we review spin–structure correlations in Nature’s water-splitting catalyst. The catalytic cycle of the Mn4O5Ca cofactor can be described in terms of spin-dependent reactivity. The lower “inactive” S states of the catalyst, S0 and S1, are characterized by low-spin ground states, SGS = 1/2 and SGS = 0. This is connected to the “open cubane” topology of the inorganic core in these states. The S2 state exhibits structural and spin heterogeneity in the form of two interconvertible isomers and is identified as the spin–switching point of the catalytic cycle. The first S2 state form is an open...

Determination and prediction of the magnetic anisotropy of Mn ions

Abstract: This tutorial is dedicated to the investigation of magnetic anisotropy using both electron paramagnetic resonance (EPR) spectroscopy for its experimental determination and quantum chemistry for its theoretical prediction. Such an approach could lead to the definition of magneto-structural correlation essential for the rational design of complexes with targeted magnetic properties or for the identification of unknown reactive metallic species involved in catalysis. To illustrate this combined approach the high spin MnII, MnIII and MnIV ions have been taken as specific examples. The first part deals with the analysis of the EPR experiments as a function of the ions under investigation and the conditions of the measurements, specifically: (i) EPR spectra recorded under high vs. low frequency conditions with respect to magnetic anisotropy, (ii) EPR spectra of non-integer (Kramers) vs. integer (non-Kramers) spin states and (iii) mono- vs. multi-frequency EPR spectra. In the second part, two main quantum chemical approaches, which have proven their capability to predict magnetic anisotropy, are described. More importantly, these calculations give access to the different contributions of zero field splitting, key information for the full understanding of magnetic anisotropy. The last part demonstrates that such a combined experimental and theoretical approach allows for the definition of magneto-structural correlations.

Where Does the Density Localize? Convergent Behavior for Global Hybrids, Range Separation, and DFT+U

Abstract: Approximate density functional theory (DFT) suffers from many-electron self-interaction error, otherwise known as delocalization error, that may be diagnosed and then corrected through elimination of the deviation from exact piecewise linear behavior between integer electron numbers. Although paths to correction of energetic delocalization error are well-established, the impact of these corrections on the electron density is less well-studied. Here, we compare the effect on density delocalization of DFT+U (i.e., semilocal DFT augmented with a Hubbard U correction), global hybrid tuning, and range-separated hybrid tuning on a diverse test set of 32 transition metal complexes and observe the three methods to have qualitatively equivalent effects on the ground state density. Regardless of valence orbital diffuseness (i.e., from 2p to 5p), ligand electronegativity (i.e., from Al to O), basis set (i.e., plane wave versus localized basis set), metal (i.e., Ti, Fe, Ni), and spin state, or tuning method, we consi...

Direct evidence for minority spin gap in the Co2MnSi Heusler alloy

Abstract: Half metal magnets are of great interest in the field of spintronics because of their potential full spin polarization at the Fermi level (E F) and low magnetization damping. The high Curie temperature and the predicted 0. 7 eV minority spin gap make the Co 2 MnSi Heusler compound very promising for applications. We investigated the half-metallic magnetic character of this compound using spin-resolved photoemission , ab initio calculation , and ferromagnetic resonance. At the surface of Co 2 MnSi , a gap in the minority spin channel is observed , leading to 100% spin polarization. However , this gap is 0. 3 eV below E F , and a minority spin state is observed at E F. We show that a minority spin gap at E F can nevertheless be recovered either by changing the chemical composition of the compound or by covering the surface by Mn , MnSi , or MgO. This spin-gap recovery results in extremely small damping coefficients , reaching values as low as 7 × 10 −4 .

Engineered Mott ground state in a LaTiO3+δ/LaNiO3 heterostructure

Abstract: In pursuit of creating cuprate-like electronic and orbital structures, artificial heterostructures based on LaNiO3 have inspired a wealth of exciting experimental and theoretical results. However, to date there is a very limited experimental understanding of the electronic and orbital states emerging from interfacial charge transfer and their connections to the modified band structure at the interface. Towards this goal, we have synthesized a prototypical superlattice composed of a correlated metal LaNiO3 and a doped Mott insulator LaTiO(3+δ), and investigated its electronic structure by resonant X-ray absorption spectroscopy combined with X-ray photoemission spectroscopy, electrical transport and theory calculations. The heterostructure exhibits interfacial charge transfer from Ti to Ni sites, giving rise to an insulating ground state with orbital polarization and e(g) orbital band splitting. Our findings demonstrate how the control over charge at the interface can be effectively used to create exotic electronic, orbital and spin states.

Surface-induced spin state locking of the [Fe(H2B(pz)2)2(bipy)] spin crossover complex.

Abstract: Temperature- and coverage-dependent studies of the Au(1 1 1)-supported spin crossover Fe(II) complex (SCO) of the type [Fe(H2B(pz)2)2(bipy)] with a suite of surface-sensitive spectroscopy and microscopy tools show that the substrate inhibits thermally induced transitions of the molecular spin state, so that both high-spin and low-spin states are preserved far beyond the spin transition temperature of free molecules. Scanning tunneling microscopy confirms that [Fe(H2B(pz)2)2(bipy)] grows as ordered, molecular bilayer islands at sub-monolayer coverage and as disordered film at higher coverage. The temperature dependence of the electronic structure suggest that the SCO films exhibit a mixture of spin states at room temperature, but upon cooling below the spin crossover transition the film spin state is best described as a mix of high-spin and low-spin state molecules of a ratio that is constant. This locking of the spin state is most likely the result of a substrate-induced conformational change of the interfacial molecules, but it is estimated that also the intra-atomic electron–electron Coulomb correlation energy, or Hubbard correlation energy U, could be an additional contributing factor.

Control of the Ultrafast Photoinduced Magnetization across the Morin Transition in DyFeO 3

Abstract: Excitation of the collinear compensated antiferromagnet DyFeO_{3} with a single 60 fs laser pulse triggers a phase transition across the Morin point into a noncollinear spin state with a net magnetization. Time-resolved imaging of the magnetization dynamics of this process reveals that the pulse first excites the spin oscillations upon damping of which the noncollinear spin state emerges. The sign of the photoinduced magnetization is defined by the relative orientation of the pump polarization and the direction of the antiferromagnetic vector in the initial collinear spin state.

Vector magnetometry using silicon vacancies in 4H-SiC at ambient conditions

Abstract: Point defects in solids promise precise measurements of various quantities. Especially magnetic field sensing using the spin of point defects has been of great interest recently. When optical readout of spin states is used, point defects achieve optical magnetic imaging with high spatial resolution at ambient conditions. Here, we demonstrate that genuine optical vector magnetometry can be realized using the silicon vacancy in SiC, which has an uncommon S=3/2 spin. To this end, we develop and experimentally test sensing protocols based on a reference field approach combined with multi frequency spin excitation. Our works suggest that the silicon vacancy in an industry-friendly platform, SiC, has potential for various magnetometry applications at ambient conditions.

Electron Spin Relaxation Can Enhance the Performance of a Cryptochrome-Based Magnetic Compass Sensor

Abstract: The radical pair model of the avian magnetoreceptor relies on long-lived electron spin coherence. Dephasing, resulting from interactions of the spins with their fluctuating environment, is generally assumed to degrade the sensitivity of this compass to the direction of the Earth's magnetic field. Here we argue that certain spin relaxation mechanisms can enhance its performance. We focus on the flavin–tryptophan radical pair in cryptochrome, currently the only candidate magnetoreceptor molecule. Correlation functions for fluctuations in the distance between the two radicals in Arabidopsis thaliana cryptochrome 1 were obtained from molecular dynamics (MD) simulations and used to calculate the spin relaxation caused by modulation of the exchange and dipolar interactions. We find that intermediate spin relaxation rates afford substantial enhancements in the sensitivity of the reaction yields to an Earth-strength magnetic field. Supported by calculations using toy radical pair models, we argue that these enhancements could be consistent with the molecular dynamics and magnetic interactions in avian cryptochromes.

Spin state ordering of strongly correlating LaCoO 3 induced at ultrahigh magnetic fields

Abstract: An additional degree of freedom in cobalt oxides that makes them fascinating is the spin state of the Co${}^{3+}$ ions, which possess six $d$-shall electrons and can form configurations with spins $S$=0, 1, or 2. In the prototypical member of the family, LaCoO${}_{3}$, the ground state is believed to be insulating with the spin state $S$=0. However, there has been a great deal of controversy over the last decades about the nature of the excited states and the phases observed at higher temperatures. The authors here approach this long-standing problem by applying ultrahigh magnetic fields reaching 133 Tesla at temperatures ranging from 2 to 120 K. Surprisingly, at magnetic fields above 100 T, they find two novel magnetic phases that are identified as spin-state crystalline states, possibly with some orbital ordering.

Surface Landau levels and spin states in bismuth (111) ultrathin films

Abstract: The development of next-generation electronics is much dependent on the discovery of materials with exceptional surface-state spin and valley properties. Because of that, bismuth has attracted a renewed interest in recent years. However, despite extensive studies, the intrinsic electronic transport properties of Bi surfaces are largely undetermined due to the strong interference from the bulk. Here we report the unambiguous determination of the surface-state Landau levels in Bi (111) ultrathin films using scanning tunnelling microscopy under magnetic fields perpendicular to the surface. The Landau levels of the electron-like and the hole-like carriers are accurately characterized and well described by the band structure of the Bi (111) surface from density functional theory calculations. Some specific surface spin states with a large g-factor are identified. Our findings shed light on the exploiting surface-state properties of Bi for their applications in spintronics and valleytronics.

Synthetic gauge fields in synthetic dimensions: interactions and chiral edge modes

Abstract: Synthetic ladders realized with one-dimensional alkaline-earth(-like) fermionic gases and subject to a gauge field represent a promising environment for the investigation of quantum Hall physics with ultracold atoms. Using density-matrix renormalization group calculations, we study how the quantum Hall-like chiral edge currents are affected by repulsive atom–atom interactions. We relate the properties of such currents to the asymmetry of the spin resolved momentum distribution function, a quantity which is easily addressable in state-of-art experiments. We show that repulsive interactions significantly enhance the chiral currents. Our numerical simulations are performed for atoms with two and three internal spin states.

The electronic structure and spin states of 2D graphene/VX2 (X = S, Se) heterostructures

Abstract: The structural, magnetic and electronic properties of 2D VX2 (X = S, Se) monolayers and graphene/VX2 heterostructures were studied using a DFT+U approach. It was found that the stability of the 1T phases of VX2 monolayers is linked to strong electron correlation effects. The study of vertical junctions comprising of graphene and VX2 monolayers demonstrated that interlayer interactions lead to the formation of strong spin polarization of both graphene and VX2 fragments while preserving the linear dispersion of graphene-originated bands. It was found that the insertion of Mo atoms between the layers leads to n-doping of graphene with a selective transformation of graphene bands keeping the spin-down Dirac cone intact.

Solvent-induced structural diversity in tetranuclear Ni(ii) Schiff-base complexes: the first Ni4 single-molecule magnet with a defective dicubane-like topology.

Abstract: Two tetranuclear NiII complexes, namely [Ni4(L)4(CH3OH)3(H2O)]·CH3OH (1) and (Pr3NH)2[Ni4(L)4(CH3COO)2] (2, Pr3N = tripropylamine), were synthesized from a tridentate Schiff base ligand H2L (2-[(E)-(2-hydroxybenzylidene)amino]phenol) and Ni(CH3COO)2·4H2O, using different solvents and their ratios (CH3OH and/or CH2Cl2). The prepared Ni4 complexes are of different structural types, involving an Ni4O4 cubane-like core (1) and Ni4O6 defective dicubane-like core (2), with all the Ni atoms hexacoordinated. The complexes were characterized by elemental analysis, FT-IR spectroscopy, variable temperature and field magnetic measurements, and single crystal X-ray analysis. The DFT and CASSCF/NEVPT2 theoretical calculations were utilized to reveal information about the isotropic exchange parameters (Jij) and single-ion zero-field splitting parameters (Di, Ei). The variable temperature magnetic data suggested the competition of the antiferromagnetic and ferromagnetic intracluster interactions in compound 1, which is in contrast to compound 2, where all intracluster interactions are ferromagnetic resulting in the ground spin state S = 4 with an easy-axis type of anisotropy quantified by the axial zero-field splitting parameter D = −0.81 cm−1. This resulted in the observation of a field-induced slow-relaxation of magnetization (U = 3.3–6.7 K), which means that the complex 2 represents the first Ni4 single-molecule magnet with the defective dicubane-like topology.

Ordering phenomena of high-spin/low-spin states in stepwise spin-crossover materials described by the ANNNI model

Abstract: We study the complex spin-state switching mechanism in a bistable molecular crystal undergoing a stepwise conversion from high-spin to low-spin states at thermal equilibrium as well as during the relaxation process from the photoinduced metastable state. We experimentally evidence that such steps are associated with complex types of long-range and short-range ordering phenomena, resulting from the occupational modulation of bistable molecular magnetic states. The conversion is then described by using two order parameters: the totally symmetric average high spin fraction and the symmetry breaking ordering parameter. The use of the anisotropic next-nearest-neighbor Ising (ANNNI) model allows us to describe the microscopic origin of the ordering, and Monte Carlo simulations reproduce the observed stepwise thermal phase transition as well as the stepwise relaxation from the photoinduced high-spin state to the low-spin state.

Unconventional high-Tc superconductivity in fullerides

Abstract: A3C60 molecular superconductors share a common electronic phase diagram with unconventional high-temperature superconductors such as the cuprates: superconductivity emerges from an antiferromagnetic strongly correlated Mott-insulating state upon tuning a parameter such as pressure (bandwidth control) accompanied by a dome-shaped dependence of the critical temperature, Tc However, unlike atom-based superconductors, the parent state from which superconductivity emerges solely by changing an electronic parameter-the overlap between the outer wave functions of the constituent molecules-is controlled by the C60 (3-) molecular electronic structure via the on-molecule Jahn-Teller effect influence of molecular geometry and spin state. Destruction of the parent Mott-Jahn-Teller state through chemical or physical pressurization yields an unconventional Jahn-Teller metal, where quasi-localized and itinerant electron behaviours coexist. Localized features gradually disappear with lattice contraction and conventional Fermi liquid behaviour is recovered. The nature of the underlying (correlated versus weak-coupling Bardeen-Cooper-Schrieffer theory) s-wave superconducting states mirrors the unconventional/conventional metal dichotomy: the highest superconducting critical temperature occurs at the crossover between Jahn-Teller and Fermi liquid metal when the Jahn-Teller distortion melts.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.