Electronic transport properties of single-molecule junctions have been widely measured by several techniques, including mechanically controllable break junctions, electromigration break junctions, and by means of scanning tunneling microscopes. In parallel, many theoretical tools have been developed and refined for describing such transport properties and for obtaining numerical predictions. Most prominent among these theoretical tools are those based upon density functional theory. In this review, theory and experiment are critically compared, and this confrontation leads to several important conclusions. The theoretically predicted trends nowadays reproduce the experimental findings well for series of molecules with a single well-defined control parameter, such as the length of the molecules. The quantitative agreement between theory and experiment usually is less convincing, however. Two main sources for the quantitative discrepancies can be identified. Experimentally, the atomic structure of the junction typically realized in the measurement is not well known, so simulations rely on plausible scenarios. In theory, correlation effects can be included only in approximations that are difficult to control for experimentally relevant situations. Therefore, one typically expects qualitative agreement with present modeling tools; in exceptional cases a quantitative agreement has already been achieved. For further progress, benchmark systems are required that are sufficiently well defined by experiment to allow quantitative testing of the approximation schemes underlying the theoretical modeling. Several key experiments can be identified suggesting that the present description may even be qualitatively incomplete in some cases. Such key experimental observations and their current models are also discussed here, leading to several suggestions for extensions of the models toward including dynamic image charges, electron correlations, and polaron formation.

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Advances and challenges in single-molecule electron transport

Emergent electronic phenomena in iron-based superconductors have been at the forefront of condensed matter physics for more than a decade. Much has been learned about the origins and intertwined roles of ordered phases, including nematicity, magnetism, and superconductivity, in this fascinating class of materials. In recent years, focus has been centered on the peculiar and highly unusual properties of FeSe and its close cousins. This family of materials has attracted considerable attention due to the discovery of unexpected superconducting gap structures, a wide range of superconducting critical temperatures, and evidence for nontrivial band topology, including associated spin-helical surface states and vortex-induced Majorana bound states. Here, we review superconductivity in iron chalcogenide superconductors, including bulk FeSe, doped bulk FeSe, FeTe1−xSex, intercalated FeSe materials, and monolayer FeSe and FeTe1−xSex on SrTiO3. We focus on the superconducting properties, including a survey of the relevant experimental studies, and a discussion of the different proposed theoretical pairing scenarios. In the last part of the paper, we review the growing recent evidence for nontrivial topological effects in FeSe-related materials, focusing again on interesting implications for superconductivity.

https://www.mdpi.com/2073-8994/12/9/1402/pdf

On the Remarkable Superconductivity of FeSe and Its Close Cousins

Atomic-scale magnetic moments in contact with superconductors host rich physics based on the emergence of Yu–Shiba–Rusinov (YSR) magnetic bound states within the superconducting condensate. Here, w...

Tunable Spin-Superconductor Coupling of Spin 1/2 Vanadyl Phthalocyanine Molecules.

We investigate the spectral evolution in different metal phthalocyanine molecules on NbSe2 surface using scanning tunnelling microscopy (STM) as a function of the coupling with the substrate. For manganese phthalocyanine (MnPc), we demonstrate a smooth spectral crossover from Yu-Shiba-Rusinov (YSR) bound states to spin-flip excitations. This has not been observed previously and it is in contrast to simple theoretical expectations. We corroborate the experimental findings using numerical renormalization group calculations. Our results provide fundamental new insight on the behavior of atomic scale magnetic/SC hybrid systems, which is important, for example, for engineered topological superconductors and spin logic devices.

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Observation of Coexistence of Yu-Shiba-Rusinov States and Spin-Flip Excitations.

Magnetic materials interfaced with superconductors may reveal new physical phenomena with potential for quantum technologies. The use of molecules as magnetic components has already shown great promise, but the diversity of properties offered by the molecular realm remains largely unexplored. Here we investigate a submonolayer of tetrairon(iii) propeller-shaped single molecule magnets deposited on a superconducting lead surface. This material combination reveals a strong influence of the superconductor on the spin dynamics of the single molecule magnet. It is shown that the superconducting transition to the condensate state switches the single molecule magnet from a blocked magnetization state to a resonant quantum tunnelling regime. Our results open perspectives to control single molecule magnetism via superconductors and to use single molecule magnets as local probes of the superconducting state. A superconducting transition is used to switch a single molecule magnet from a blocked magnetization state to a resonant quantum tunnelling regime

Quantum dynamics of a single molecule magnet on superconducting Pb(111).

The exchange scattering at magnetic adsorbates on superconductors gives rise to Yu-Shiba-Rusinov (YSR) bound states. Depending on the strength of the exchange coupling, the magnetic moment perturbs the Cooper pair condensate only weakly, resulting in a free-spin ground state, or binds a quasiparticle in its vicinity, leading to a (partially) screened spin state. Here, we use the flexibility of Fe-porphin (FeP) molecules adsorbed on a Pb(111) surface to reversibly and continuously tune between these distinct ground states. We find that the FeP moment is screened in the pristine adsorption state. Approaching the tip of a scanning tunneling microscope, we exert a sufficiently strong attractive force to tune the molecule through the quantum phase transition into the free-spin state. We ascertain and characterize the transition by investigating the transport processes as function of tip-molecule distance, exciting the YSR states by single-electron tunneling as well as (multiple) Andreev reflections.

https://link.aps.org/accepted/10.1103/PhysRevLett.121.196803

Tuning the Coupling of an Individual Magnetic Impurity to a Superconductor: Quantum Phase Transition and Transport.

Magnetic adsorbates on superconductors induce a Kondo resonance outside and Yu-Shiba-Rusinov (YSR) bound states inside the superconducting energy gap. When probed by scanning tunneling spectroscopy, the associated differential-conductance spectra frequently exhibit characteristic bias-voltage asymmetries. Here, we observe correlated variations of Kondo and YSR asymmetries across an Fe-porphyrin molecule adsorbed on Pb(111). We show that both asymmetries originate in interfering tunneling paths via a spin-carrying orbital and the highest occupied molecular orbital (HOMO). Strong evidence for this model comes from nodal planes of the HOMO, where tunneling reveals symmetric Kondo and YSR resonances. Our results establish an important mechanism for the asymmetries of Kondo and YSR line shapes.

Interfering Tunneling Paths through Magnetic Molecules on Superconductors: Asymmetries of Kondo and Yu-Shiba-Rusinov Resonances.

Historically, electron spin resonance (ESR) has provided excellent insight into the electronic, magnetic, and chemical structure of samples hosting spin centers. In particular, the hyperfine interaction between the electron and the nuclear spins yields valuable structural information about these centers. In recent years, the combination of ESR and scanning tunneling microscopy (ESR-STM) has allowed to acquire such information about individual spin centers of magnetic atoms bound atop a surface, while additionally providing spatial information about the binding site. Here, we conduct a full angle-dependent investigation of the hyperfine splitting for individual hydrogenated titanium atoms on MgO/Ag(001) by measurements in a vector magnetic field. We observe strong anisotropy in both the g factor and the hyperfine tensor. Combining the results of the hyperfine splitting with the symmetry properties of the binding site obtained from STM images and a basic point charge model allows us to predict the shape of the electronic ground state configuration of the titanium atom. Relying on experimental values only, this method paves the way for a new protocol for electronic structure analysis for spin centers on surfaces.

https://pubs.acs.org/doi/pdf/10.1021/acs.nanolett.2c02783

Experimental Determination of a Single Atom Ground State Orbital through Hyperfine Anisotropy

Atomically engineered artificial lattices are a useful tool for simulating complex quantum phenomena, but have so far been limited to the study of Hamiltonians where electron–electron interactions do not play a role. However, it is precisely the regime in which these interactions do matter where computational times lend simulations a critical advantage over numerical methods. Here, we propose a platform for constructing artificial matter that relies on the confinement of field-emission resonances, a class of vacuum-localized discretized electronic states. We use atom manipulation of surface vacancies in a chlorine-terminated Cu(100) surface to reveal square patches of the underlying metal, thereby creating atomically precise potential wells that host particle-in-a-box modes. By adjusting the dimensions of the confining potential, we can access states with different quantum numbers, making these patches attractive candidates as quantum dots or artificial atoms. We demonstrate that the lifetime of electrons in these engineered states can be extended and tuned through modification of the confining potential, either via atomic assembly or by changing the tip–sample distance. We also demonstrate control over a finite range of state filling, a parameter which plays a key role in the evolution of quantum many-body states. We model the transport through the localized state to disentangle and quantify the lifetime-limiting processes, illustrating the critical dependence of the electron lifetime on the properties of the underlying bulk band structure. The interplay with the bulk bands gives rise to negative differential resistance, leading to possible applications in engineering custom atomic-scale resonant tunnelling diodes, which exhibit similar current–voltage characteristics.

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Confined Vacuum Resonances as Artificial Atoms with Tunable Lifetime

Diﬀerential conductance spectroscopy performed in the high bias regime—in which the applied voltage exceeds the sample work function—is a poor measure of the local density of states due to the eﬀects of the changing tunnel barrier. Additionally, the large applied voltage oftentimes makes constant-height measurement experimentally impractical, lending constant-current spectroscopy an advantageous edge; but the diﬀerential conductance in that case is even further removed from the local density of states due to the changing tip height. Here, we present a normalization scheme for extracting the local density of states from high bias scanning tunneling spectroscopy, obtained in either constant-current or constant-height mode. We extend this model to account for the eﬀects of the in-plane momentum of the probed states to the overall current. We demonstrate the validity of the proposed scheme by applying it to laterally conﬁned ﬁeld-emission resonances, which appear as peak-shaped spectroscopic features with a well-deﬁned in-plane momentum.

http://link.aps.org/pdf/10.1103/PhysRevB.107.035406

Laëtitia Farinacci

Papers

Tuning the Coupling of an Individual Magnetic Impurity to a Superconductor: Quantum Phase Transition and Transport.

Interfering Tunneling Paths through Magnetic Molecules on Superconductors: Asymmetries of Kondo and Yu-Shiba-Rusinov Resonances.

Experimental Determination of a Single Atom Ground State Orbital through Hyperfine Anisotropy

Confined Vacuum Resonances as Artificial Atoms with Tunable Lifetime

Normalization procedure for obtaining the local density of states from high-bias scanning tunneling spectroscopy