Ultrahigh spin thermopower and pure spin current in a single-molecule magnet.
Ontology highlight
ABSTRACT:
SUBMITTER: Luo B
PROVIDER: S-EPMC3928577 | biostudies-other | 2014
REPOSITORIES: biostudies-other
Similar Datasets
Project description:In molecular spintronics, the spin state of a molecule may be switched on and off by changing the molecular structure. Here, we switch on and off the molecular spin of a double-decker bis(phthalocyaninato)terbium(III) complex (TbPc?) adsorbed on an Au(111) surface by applying an electric current via a scanning tunnelling microscope. The dI/dV curve of the tunnelling current recorded onto a TbPc? molecule shows a Kondo peak, the origin of which is an unpaired spin of a ?-orbital of a phthalocyaninato (Pc) ligand. By applying controlled current pulses, we could rotate the upper Pc ligand in TbPc?, leading to the disappearance and reappearance of the Kondo resonance. The rotation shifts the molecular frontier-orbital energies, quenching the ?-electron spin. Reversible switching between two stable ligand orientations by applying a current pulse should make it possible to code information at the single-molecule level.
| S-EPMC3072104 | biostudies-literature
Project description:Structural, spectroscopic and magnetic methods have been used to characterize the tris(carbene)borate compound PhB(MesIm)3Mn?N as a four-coordinate manganese(IV) complex with a low spin (S = 1/2) configuration. The slow relaxation of the magnetization in this complex, i.e. its single-molecule magnet (SMM) properties, is revealed under an applied dc field. Multireference quantum mechanical calculations indicate that this SMM behavior originates from an anisotropic ground doublet stabilized by spin-orbit coupling. Consistent theoretical and experiment data show that the resulting magnetization dynamics in this system is dominated by ground state quantum tunneling, while its temperature dependence is influenced by Raman relaxation.
| S-EPMC5058364 | biostudies-literature
Project description:Triplet diradicals have attracted tremendous attention due to their promising application in organic spintronics, organic magnets and spin filters. However, very few examples of triplet diradicals with singlet-triplet energy gaps (ΔE ST) over 0.59 kcal mol-1 (298 K) have been reported to date. In this work, we first proved that the dianion of 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (2,7-tBu2-PTO) was a triplet ground state diradical in the magnesium complex 1 with a singlet-triplet energy gap ΔE ST = 0.94 kcal mol-1 (473 K). This is a rare example of stable diradicals with singlet-triplet energy gaps exceeding the thermal energy at room temperature (298 K). Moreover, the iron analog 2 containing the 2,7-tBu2-PTO diradical dianion was isolated, which was the first single-molecule magnet bridged by a diradical dianion. When 2 was doubly reduced to the dianion salt 2K2, single-molecule magnetism was switched off, highlighting the importance of diradicals in single-molecule magnetism.
| S-EPMC8317668 | biostudies-literature
Project description:Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.
| S-EPMC7935416 | biostudies-literature
Project description:The air stable complex [(PNP)FeCl(2)] (1) (PNP = N[2-P(CHMe(2))(2)-4-methylphenyl](2)(-)), prepared from one-electron oxidation of [(PNP)FeCl] with ClCPh(3), displays an unexpected S = 3/2 to S = 5/2 transition above 80 K as inferred by the dc SQUID magnetic susceptibility measurement. The ac SQUID magnetization data, at zero field and between frequencies 10 and 1042 Hz, clearly reveal complex 1 to have frequency dependence on the out-of-phase signal and thus being a single molecular magnet with a thermally activated barrier of U(eff) = 32-36 cm(-1) (47-52 K). Variable-temperature Mössbauer data also corroborate a significant temperature dependence in ? and ?E(Q) values for 1, which is in agreement with the system undergoing a change in spin state. Likewise, variable-temperature X-band EPR spectra of 1 reveals the S = 3/2 to be likely the ground state with the S = 5/2 being close in energy. Multiedge XAS absorption spectra suggest the electronic structure of 1 to be highly covalent with an effective iron oxidation state that is more reduced than the typical ferric complexes due to the significant interaction of the phosphine groups in PNP and Cl ligands with iron. A variable-temperature single crystal X-ray diffraction study of 1 collected between 30 and 300 K also reveals elongation of the Fe-P bond lengths and increment in the Cl-Fe-Cl angle as the S = 5/2 state is populated. Theoretical studies show overall similar orbital pictures except for the d(z(2)) orbital, which has the most sensitivity to change in the geometry and bonding, where the quartet ((4)B) and the sextet ((6)A) states are close in energy.
| S-EPMC3495239 | biostudies-literature
Project description:Non-local spin injection in lateral spin valves generates a pure spin current which is a diffusive flow of spins (i.e. spin angular momentums) with no net charge flow. The diffusive spins lose phase coherency in precession while undergoing frequent collisions and these events lead to a broad distribution of the dwell time in a transport channel between the injector and the detector. Here we show the lateral spin-valves with dual injectors enable us to detect a genuine in-plane precession signal from the Hanle effect, demonstrating the phase coherency in the in-plane precession is improved with an increase of the channel length. The coherency in the spin precession shows a universal behavior as a function of the normalized separation between the injector and the detector in material-independent fashion for metals and semiconductors including graphene.
| S-EPMC3432863 | biostudies-other
Project description:Metal-molecule-metal junction is a promising candidate for thermoelectric applications that utilizes quantum confinement effects in the chemically defined zero-dimensional atomic structure to achieve enhanced dimensionless figure of merit ZT. A key issue in this new class of thermoelectric nanomaterials is to clarify the sensitivity of thermoelectricity on the molecular junction configurations. Here we report simultaneous measurements of the thermoelectric voltage and conductance on Au-1,4-benzenedithiol (BDT)-Au junctions mechanically-stretched in-situ at sub-nanoscale. We obtained the average single-molecule conductance and thermopower of 0.01 G0 and 15??V/K, respectively, suggesting charge transport through the highest occupied molecular orbital. Meanwhile, we found the single-molecule thermoelectric transport properties extremely-sensitive to the BDT bridge configurations, whereby manifesting the importance to design the electrode-molecule contact motifs for optimizing the thermoelectric performance of molecular junctions.
| S-EPMC4481826 | biostudies-other
Project description:Two-dimensional topological insulators possess two counter propagating edge channels with opposite spin direction. Recent experimental progress allowed to create ferromagnetic topological insulators realizing a quantum anomalous Hall (QAH) state. In the QAH state one of the two edge channels disappears due to the strong ferromagnetic exchange field. We investigate heterostructures of topological insulators and ferromagnetic topological insulators by means of numerical transport calculations. We show that spin current flow in such heterostructures can be controlled with high fidelity. Specifically, we propose spintronic devices that are capable of creating, switching and detecting pure spin currents using the same technology. In these devices electrical currents are directly converted into spin currents, allowing a high conversion efficiency. Energy independent transport properties in combination with large bulk gaps in some topological insulator materials may allow operation even at room temperature.
| S-EPMC5080548 | biostudies-literature
Project description:Molecular junction is a chemically-defined nanostructure whose discrete electronic states are expected to render enhanced thermoelectric figure of merit suitable for energy-harvesting applications. Here, we report on geometrical dependence of thermoelectricity in metal-molecule-metal structures. We performed simultaneous measurements of the electrical conductance and thermovoltage of aromatic molecules having different anchoring groups at room temperature in vacuum. We elucidated the mutual contributions of vacuum tunnelling on thermoelectricity in the short molecular bridges. We also found stretching-induced thermoelectric voltage enhancement in thiol-linked single-molecule bridges along with absence of the pulling effects in diamine counterparts, thereby suggested that the electromechanical effect would be a rather universal phenomenon in Au-S anchored molecular junctions that undergo substantial metal-molecule contact elongation upon stretching. The present results provide a novel concept for molecular design to achieve high thermopower with single-molecule junctions.
| S-EPMC5345045 | biostudies-literature
Project description:Dy single-molecule magnets (SMMs), which have several potential uses in a variety of applications, such as quantum computing, were encapsulated in multi-walled carbon nanotubes (MWCNTs) by using a capillary method. Encapsulation was confirmed by using transmission electron microscopy (TEM). In alternating current magnetic measurements, the magnetic susceptibilities of the Dy acetylacetonato complexes showed clear frequency dependence even inside the MWCNTs, meaning that this hybrid can be used as magnetic materials in devices.
| S-EPMC5344606 | biostudies-literature