Single Magnetic Molecule Research Articles

Theory of electron spin resonance in scanning tunneling microscopy

Electron spin resonance (ESR) spectroscopy in scanning tunneling microscopy (STM) has enabled probing the electronic structure of single magnetic atoms and molecules on surfaces with unprecedented energy resolution, as well as demonstrating coherent manipulation of single spins. Despite this remarkable success, the field could still be greatly advanced by a more quantitative understanding of the ESR-STM physical mechanisms. Here, we present a theory of ESR-STM that quantitatively models not only the ESR signal itself, but also the full background tunneling current, from which the ESR signal is derived. Our theory is based on a combination of Green's function techniques to describe the electron tunneling and a quantum master equation for the dynamics of the spin system along with microwave radiation interacting with both the tunneling current and the magnetic system. We show that this theory is able to quantitatively reproduce the experimental results for a spin-1/2 system (TiH molecules on MgO) across many orders of magnitude in tunneling current, providing access to the relaxation and decoherence rates that govern the spin dynamics due to intrinsic mechanisms and to the applied bias voltage. More importantly, our work establishes that (i) sizable ESR signals, which are a measure of microwave-induced changes in the junction magnetoresistance, require surprisingly high tip spin polarizations, and (ii) the coupling of the magnetization dynamics to the microwave field gives rise to the asymmetric ESR spectra often observed in this spectroscopy. Additionally, our theory provides very specific predictions for the dependence of the relaxation and decoherence times on the bias voltage and the tip-sample distance. Finally, with the help of electromagnetic simulations, we find that the transitions in our ESR-STM experiments, in which the tunnel junction is irradiated by a nearby microwave antenna, can be driven by the ac magnetic field at the junction. Published by the American Physical Society 2024

Exchange-induced spin polarization in a single magnetic molecule junction

Many spintronic devices rely on the presence of spin-polarized currents at zero magnetic field. This is often obtained by spin exchange-bias, where an element with long-range magnetic order creates magnetized states and displaces the hysteresis loop. Here we demonstrate that exchange-split spin states are observable and usable in the smallest conceivable unit: a single magnetic molecule. We use a redox-active porphyrin as a transport channel, coordinating a dysprosium-based single-molecule-magnet inside a graphene nano-gap. Single-molecule transport in magnetic field reveals the existence of exchange-split channels with different spin-polarizations that depend strongly on the field orientation, and comparison with the diamagnetic isostructural compound and milikelvin torque magnetometry unravels the role of the single-molecule anisotropy and the molecular orientation. These results open a path to using spin-exchange in molecular electronics, and offer a method to quantify the internal spin structure of single molecules in multiple oxidation states.

Electric field tuning of magnetic states in single magnetic molecules

Single magnetic molecules may be the smallest functional magnets. An electric-field controllable spin state of magnetic molecules is of fundamental importance for applications while its realization remains challenging. To date the observed spin-electric interaction based on spin-orbit coupling or spin dipole coupling is useful to tune fine spin structures but too weak to flip the spin state. In this work, we propose a new mechanism to realize enhanced spin-electric coupling and flip the spin states by tuning the spin superexchange between local spins. Using first-principles calculations and Heisenberg Hamiltonian, we demonstrate this effect in a family of magnetic molecules, transition metallic Porphyrins. We show that their d-{\pi} and {\pi}-{\pi} spin superexchange couplings are determined by the relative energies of d and {\pi} electronic states, which are sensitive to the applied electric field. Therefore, applying electric field can tune a wide range of magnetic ground states, including ferromagnetic, ferrimagnetic, and antiferromagnetic configurations. This spin-electric coupling may provide a new approach for designing and controlling molecular spintronics.

Molecular engineering of an inverse hexacopper(II) coordination complex with a photoactive metallacyclophane centroligand as prototype of a magnetic photoswitch

A primary goal of molecular spintronics is detecting the response of the spins from a single magnetic molecule to an external stimulus and, eventually, being able to implement logic quantum memory capabilities for information data storage and processing applications in quantum computation. Having this in mind, a novel hexanuclear oxamatocopper(II) complex of formula {[Cu2(naba)2][Cu(pmdien)]4}(ClO4)4·8H2O (2) [naba = N,N'-1,5-naphthalenebis(oxamate) and pmdien = N,N,N’,N”,N”-pentamethyldiethylenetriamine] has been prepared by the reaction of stoichiometric amounts of (nBu4N)4[Cu2(naba)2] · 4H2O (1) (nBu4N+ = tetra-n-butylammonium cation) and [Cu(pmdien)](ClO4)2 (1:4 molar ratio) in water. 2 exhibits a ladder-like “dimer-of-trinuclears” structure featuring a photoactive dicopper(II) naphthalenophane core acting as inverse coordination centre (centroligand) towards four peripheral [Cu(pmdien)]2+ groups through the outer amidate/carboxylate oxygen atoms of the oxamato fragments. 2 undergoes a unique magnetic photoswitching ON/OFF behaviour upon UV light irradiation because of an intramolecular (“pseudo-bimolecular”) photocycloaddition of the two facing naphthalene spacers through the more reactive carbon atoms at the 1,4 and 1’,4’ positions of the benzene rings to afford the putative [4 + 4] cycloaddition product c-2. Hence, the two oxamato-bridged S = 1/2 CuII3 linear units antiferromagnetically coupled within the CuII6 precursor (2, ON state) become magnetically uncoupled in the corresponding [4 + 4] photocycloaddition product (c-2, OFF state) [jeff = –2.13 (2) and 0 cm−1 (c-2); H = – jeffSA.SB with SA = SB = 1/2]. This new example of inverse coordination complex constitutes thus a potential candidate to molecular magnetic photoswitch in the “bottom-up” approach to nanometer-scale spintronic and quantum computing devices.

First-principles determination of magnetic properties of CoCp2 on the Cr(001) surface

Through density-functional calculations, we systematically studied the exchange bias effect of the antiferromagnetic Cr(001) substrate on a single magnetic molecule $\mathrm{Co}{\mathrm{Cp}}_{2}$. The magnetic moment and magnetic anisotropy of $\mathrm{Co}{\mathrm{Cp}}_{2}$ are largely tuned by the charge transfer between the molecule and substrate. A large exchange energy of \ensuremath{\sim}94 meV is found, which essentially pins the spin orientation of $\mathrm{Co}{\mathrm{Cp}}_{2}$. This makes $\mathrm{Co}{\mathrm{Cp}}_{2}/\mathrm{Cr}(001)$ an ideal combination for quantum sensing as its quantum spin states are well decoupled from those of the target magnetic entities. This work paves a way for the development of local quantum sensing with scanning probe techniques.

Yu-Shiba-Rusinov states of a single magnetic molecule in ans-wave superconductor

We use the numerical renormalization group theory to investigate the Yu-Shiba-Rusinov (YSR) bound state properties of single magnetic molecules placed in an s-wave superconducting substrate. The molecule consist of a large core spin and a single orbital, coupled via an exchange interaction. The critical Coulomb interaction for the singlet/doublet transition decreases in the presence of this exchange interaction for both ferro and anti-ferromagnetic couplings. The number of YSR states also increase to two pairs, however, in the singlet phase, one of the pairs have zero spectral weight. We explore the evolution of the in-gap states using the Anderson model. Away from the particle-hole symmetry point, the results suggest a doublet-singlet-doublet transition as the on-site energy is lowered while keeping the Coulomb interaction fixed. To understand these results, we write down an effective model for the molecule in the limit of large superconducting order parameter. Qualitatively, it explains the various phase transitions and spectral nature of the in-gap states. Finally, we analyze the effects of magnetic anisotropic fields of the core spin on in-gap states. Due to internal degrees of freedom of the spin excited states, a multitude of new states emerges within the gap. Depending on the sign and strength of the uniaxial anisotropic field, the results indicate up to three pairs of YSR states.

On-Surface Atom-by-Atom-Assembled Aluminum Binuclear Tetrabenzophenazine Organometallic Magnetic Complex.

The Kondo effect results from the interactions of the conduction electrons in a metal bulk with localized magnetic impurities. While adsorbed atop a metallic surface, the on-surface nanoscale version of this effect is observed when a single magnetic atom or a single magnetic molecule (SMM) is interacting with the conduction electrons. SMMs are commonly organometallic complexes incorporating transition-metal atoms in different oxidation states. We demonstrate how a single nonmagnetic neutral tetrabenzo[a,c,j,h]phenazine molecule can be on-surface-coordinated with exactly two aluminum metal atoms (between Al(I) and Al(II) oxidation state on the Au(111) surface) by low-temperature scanning tunneling microscope (LT-STM) single-atom manipulation. It results in a Kondo measurable localized molecular magnetic moment. This opens a new way to design SMM complexes without the need for heavy transition-metal atoms and complex ligands to stabilize the molecular coordination sphere.

Detection of Spin-Vibration States in Single Magnetic Molecules.

The spin states of magnetic molecules have advantageous attributes as carriers of quantum information. However, spin-vibration coupling in molecules causes a decay of excited spin states and a loss of spin coherence. Here, we detect excitations of spin-vibration states in single nickelocene molecules on Ag(110) with a scanning tunneling microscope. By transferring a nickelocene to the tip, the joint spin-vibration states with an adsorbed nickelocene were measured. Chemical variations in magnetic molecules offer the opportunity to tune spin-vibration coupling for controlling the spin coherence.

Electron and Cooper-pair transport across a single magnetic molecule explored with a scanning tunneling microscope

The interplay of magnetism and superconductivity gives rise to the emergence of various interesting phenomena in condensed matter physics, such as the Yu-Shiba-Rusinov in-gap modes created by local magnetic moments in superconducting hosts. Using normal-metal and superconducting tips the authors have formed contacts to an individual magnetic molecule adsorbed on a conventional superconductor. Spectroscopy of the differential conductance with tunable junction transparency has unveiled the crossover from quasiparticle tunneling, which probes the Bardeen-Cooper-Schrieffer energy gap as well as the Yu-Shiba-Rusinov levels, to the contact range where multiple Andreev reflection takes over.

Dynamical Aspects of Magnetic Switching in a Single Molecule-Based Spin Valve

The dynamics of the current-induced magnetic switching process is theoretically studied in a spin-valve device containing a single magnetic molecule of spin S 1. The analysis is performed by using the real-time diagrammatic technique in the sequential electron tunneling regime. In particular, we show that the magnetic moment of a molecule can be reversed also in the presence of intrinsic spin relaxation processes. Moreover, we discuss how the process of magnetic switching depends on a transport bias voltage as well as on some key parameters of the device.

Manipulating spins of magnetic molecules: Hysteretic behavior with respect to bias voltage

Formation of a magnetic hysteresis loop with respect to a bias voltage is investigated theoretically in a spin-valve device based on a single magnetic molecule. We consider a device consisting of two ferromagnetic electrodes bridged by a carbon nanotube, acting as a quantum dot, to which a spin-anisotropic molecule is exchange-coupled. Such a coupling allows for transfer of angular momentum between the molecule and a spin current flowing through the dot, and thus, for switching orientation of the molecular spin. We demonstrate that this current-induced switching process exhibits a hysteretic behavior with respect to a bias voltage applied to the device. The analysis is carried out with the use of the real-time diagrammatic technique in the lowest-order expansion of the tunnel coupling of the dot to electrodes. The influence of both the intrinsic properties of the spin-valve device (the spin polarization of electrodes and the coupling strength of the molecule to the dot) and those of the molecule itself (magnetic anisotropy and spin relaxation) on the size of the magnetic hysteresis loop is discussed.

Construction, physical properties and applications of low-dimensional atomic/molecular crystals

In this article, we review the representative work that has been done by Hong-Jun Gao's group in the past two decades in Institute of Physics, Chinese Academy of Sciences. The work focuses on the construction, properties and applications of low-dimensional atomic/molecular crystals, covering the following 3 aspects. 1) Construction and growth mechanisms of low-dimensional quantum structures. Firstly, we demonstrate the fabrication and growth mechanism of a seahorse shaped fractal pattern in C60-TCNQ multilayer thin films by using the ionized-cluster-beam method. Secondly, by modifying the tip of the scanning tunneling microscope (STM), we clearly resolve the six rest atoms and twelve adatoms on a Si(111)-77 unit cell, showing the highest-resolution STM images of the Si(111)-77 surface. According to this work, we investigate the adsorption and bonding of Ge atoms on Si(111)-77 at low coverages. The configurations and growth behaviors of iron phthalocyanine molecules on Au(111) surface from sub-monolayer to bilayer are also reviewed. Furthermore, we demonstrate that organic molecules bond preferentially to different facets of the Ag(775) substrate under different deposition sequences, molecular lengths, terrace widths, and step heights. This can contribute to the design of non-templated selective functionalization of nanocrystals. 2) Reversible conductance transition and spin on-off in low-dimensional quantum structures and applications in ultrahigh-density information storage. Firstly, we implement reversible, erasable, and rewritable nano-recordings on molecular thin films as a result of conductance transition. Then we demonstrate that the Kondo resonance of iron phthalocyanine molecules on an Au(111) substrate depends strongly on adsorption configuration, and the Kondo resonance of manganese phthalocyanine molecules can reversibly switch ON and OFF via attachment and detachment of single hydrogen atom to the molecule. Moreover, we achieve the site-dependent g factor of a single magnetic molecule with sub-molecular resolution, which shows an inhomogeneous distribution of the g factor within a single molecule. These results open up new routes to realizing ultrahigh-density information storage and controlling local spin properties within a single molecule. 3) Construction, physical properties and applications of graphene and other two-dimensional atomic crystals. We start with the fabrication of a wafer-size, high-quality (almost defect free), single-crystalline graphene on Ru(0001). Then we demonstrate the structure of novel two-dimensional (2D) atomic crystals of mono-element, such as silicene,germanene, hafnene, and antimonene. Last but not least, we present the formation of intrinsically patterned bi-elements 2D materials, PtSe2 and CuSe, which can serve as templates for selective self-assembly of molecules and nanoclusters, as well as dual functionalization for catalysis or other applications. The series of work done in Hong-Jun Gao's group has laid a solid foundation in the research field of low-dimensional quantum structures and their applications.

Operating Quantum States in Single Magnetic Molecules: Implementation of Grover's Quantum Algorithm.

Quantum algorithms use the principles of quantum mechanics, such as, for example, quantum superposition, in order to solve particular problems outperforming standard computation. They are developed for cryptography, searching, optimization, simulation, and solving large systems of linear equations. Here, we implement Grover's quantum algorithm, proposed to find an element in an unsorted list, using a single nuclear 3/2 spin carried by a Tb ion sitting in a single molecular magnet transistor. The coherent manipulation of this multilevel quantum system (qudit) is achieved by means of electric fields only. Grover's search algorithm is implemented by constructing a quantum database via a multilevel Hadamard gate. The Grover sequence then allows us to select each state. The presented method is of universal character and can be implemented in any multilevel quantum system with nonequal spaced energy levels, opening the way to novel quantum search algorithms.

An Iron-Porphyrin Complex with Large Easy-Axis Magnetic Anisotropy on Metal Substrate.

Easy-axis magnetic anisotropy separates two magnetic states with opposite magnetic moments, and single magnetic atoms and molecules with large easy-axis magnetic anisotropy are highly desired for future applications in high-density data storage and quantum computation. By tuning the metalation reaction between tetra-pyridyl-porphyrin molecules and Fe atoms, we have stabilized the so-called initial complex, an intermediate state of the reaction, on Au(111) substrate, and investigated the magnetic property of this complex at a single-molecule level by low-temperature scanning tunneling microscopy and spectroscopy. As revealed by inelastic electron tunneling spectroscopy in magnetic field, this Fe-porphyrin complex has magnetic anisotropy energy of more than 15 meV with its easy-axis perpendicular to the molecular plane. Two magnetic states with opposite spin directions are discriminated by the dependence of spin-flip excitation energy on magnetic field and are found to have long spin lifetimes. Our density functional theory calculations reveal that the Fe atom in this complex, decoupled from Au substrate by a weak ligand field with elongated Fe-N bonds, has a high-spin state S = 2 and a large orbital angular momentum L = 2, which give rise to easy-axis anisotropy perpendicular to the molecular plane and large magnetic anisotropy energy by spin-orbit coupling. Since the Fe atom is protected by the molecular ligand, the complex can be processed at room or even higher temperatures. The reported system may have potential applications in nonvolatile data storage, and our work demonstrates on-surface metalation reactions can be utilized to synthesize organometallic complexes with large magnetic anisotropy.

Revealing the atomic site-dependent g factor within a single magnetic molecule via the extended Kondo effect.

The site-dependent g factor of a single magnetic molecule, with intramolecular resolution, is demonstrated for the first time by low-temperature, high-magnetic-field scanning tunneling microscopy of dehydrogenated Mn-phthalocyanine molecules on Au(111). This is achieved by exploring the magnetic-field dependence of the extended Kondo effect at different atomic sites of the molecule. Importantly, an inhomogeneous distribution of the g factor inside a single molecule is revealed. Our results open up a new route to access local spin properties within a single molecule.

Switching of Magnetic Anisotropy of a Single Magnetic Molecule Observed by Scanning Tunneling Microscopy(Research)

Switching of Magnetic Anisotropy of a Single Magnetic Molecule Observed by Scanning Tunneling Microscopy(Research)

Switching of a coupled spin pair in a single-molecule junction

Single-molecule spintronics investigates electron transport through magnetic molecules that have an internal spin degree of freedom. To understand and control these individual molecules it is important to read their spin state. For unpaired spins, the Kondo effect has been observed as a low-temperature anomaly at small voltages. Here, we show that a coupled spin pair in a single magnetic molecule can be detected and that a bias voltage can be used to switch between two states of the molecule. In particular, we use the mechanically controlled break-junction technique to measure electronic transport through a single-molecule junction containing two coupled spin centres that are confined on two Co(2+) ions. Spin-orbit configuration interaction methods are used to calculate the combined spin system, where the ground state is found to be a pseudo-singlet and the first excitations behave as a pseudo-triplet. Experimentally, these states can be assigned to the absence and occurrence of a Kondo-like zero-bias anomaly in the low-temperature conductance data, respectively. By applying finite bias, we can repeatedly switch between the pseudo-singlet state and the pseudo-triplet state.

Quasiparticle Interference around a Magnetic Impurity on a Surface with Strong Spin-Orbit Coupling

On surfaces with strong spin-orbit coupling, backscattering is forbidden since it requires flipping of the spin of the electron. It has been proposed that the forbidden scattering channels in such systems can be activated if time reversal symmetry is locally broken, for example, by a magnetic scattering center. Scanning tunneling spectroscopic maps of quasiparticle interference patterns around a single magnetic MnPc molecule on a Bi(110) surface reveal only spin-conserving scattering events. Simulations based on the Green's functions approach confirm that the charge-density interference patterns are unaffected by the magnetic state of the impurity. A fingerprint of backscattering processes appears, however, in the magnetization patterns, suggesting that only spin-polarized measurements can access this information.

Cotunneling theory of atomic spin inelastic electron tunneling spectroscopy

We propose cotunneling as the microscopic mechanism that makes possible inelastic electron spectroscopy of magnetic atoms in surfaces for a wide range of systems, including single magnetic adatoms, molecules and molecular stacks. We describe electronic transport between the scanning tip and the conducting surface through the magnetic system (MS) with a generalized Anderson model, without making use of effective spin models. Transport and spin dynamics are described with an effective cotunneling Hamiltonian in which the correlations in the magnetic system are calculated exactly and the coupling to the electrodes is included up to second order in the tip-MS and MS-substrate. In the adequate limit our approach is equivalent to the phenomenological Kondo exchange model that successfully describe the experiments . We apply our method to study in detail inelastic transport in two systems, stacks of Cobalt Phthalocyanines and a single Mn atom on Cu$_2$N. Our method accounts both, for the large contribution of the inelastic spin exchange events to the conductance and the observed conductance asymmetry.

Spin dynamics of current-driven single magnetic adatoms and molecules

A scanning tunneling microscope can probe the inelastic spin excitations of a single magnetic atom in a surface via spin-flip assisted tunneling in which transport electrons exchange spin and energy with the atomic spin. If the inelastic transport time, defined as the average time elapsed between two inelastic spin flip events, is shorter than the atom spin relaxation time, the STM current can drive the spin out of equilibrium. Here we model this process using rate equations and a model Hamiltonian that describes successfully spin flip assisted tunneling experiments, including a single Mn atom, a Mn dimer and Fe Phthalocyanine molecules. When the STM current is not spin polarized, the non-equilibrium spin dynamics of the magnetic atom results in non-monotonic $dI/dV$ curves. In the case of spin polarized STM current, the spin orientation of the magnetic atom can be controlled parallel or anti-parallel to the magnetic moment of the tip. Thus, spin polarized STM tips can be used both to probe and to control the magnetic moment of a single atom.