Fe Adatoms Research Articles

Single-atom catalysts on ceria substrates: Exploring cluster and surface effects on methane activation

The activation of methane (CH4) is a critical step in its conversion to high value products, which require the use of catalysts due to the higher stability of the C-H bond. In this study, we combined density functional theory calculations and the unit bond index-quadratic exponential potential approximation to investigate the first CH4 dehydrogenation in the TM/(CeO2)10 system, where TM represents a single transition-metal specie (Fe, Co, Ni, Cu) supported in the compact (CeO2)10 cluster. In addition, substrate size effects will be addressed by comparing our results with previous surface science studies by our group. We found a direct correlation between the magnitude of the TM adsorption energy on the CeO2 substrates (hollow and bridge sites) and the magnitude of charge transfer from the TM adatoms to the substrates, while CH4 has a weaker physisorption binding energy to the ceria cluster and the surface substrates. Molecular fragments derived from CH4 (CH3 and H) bind through chemisorption interactions to the TM and O sites, respectively. The estimated energy barrier for the cleavage of the C-H bond is lower when the reaction occurs in the cluster rather than on the surface. The molecular fragments exhibited better stabilization on cluster substrates, resulting in an exergonic dehydrogenation reaction; whereas, for surfaces, the reaction was endergonic. Among the selected TM species, Fe and Co adatoms are promising candidates for the first CH4 dehydrogenation on CeO2 substrates, which can be explained by the magnitude of the metal-support interaction and stabilization of the CH3 specie, which results in the lowest barriers among the evaluated transition metals.

Computational demystification of iron carbonyls formation under syngas environment

Iron pentacarbonyl (IPC) gas forms upon the reaction of carbon monoxide with Fe containing metallic surfaces under gas reforming conditions. IPC formation can sometimes reach alarming levels that cause metal loss, pipeline thinning corrosion, catalyst poisoning, and contamination of sensitive industrial equipment. In this work, we demystify using multiscale computational modeling the mechanism of Iron pentacarbonyl formation: Density functional theory (DFT) is used to explore various catalytic reactions that involve a Fe adatom reacting with adsorbed carbon monoxide. Our calculated carbonyls desorption barriers on a perfect and clean Fe surface are too high to allow the carbonyls to form then desorb at temperatures <500 K at the rates reported experimentally. Most importantly, our calculations indicate that a high CO surface coverage, in addition to the presence of Fe adatoms, favors carbonyl formation and its desorption towards the flowing gas medium. Using insights extracted from ab initio molecular dynamics simulations, we propose that the most plausible IPC formation mechanism consists of: (1) on surface reactions of adsorbed CO molecules with an Fe adatom to form iron tricarbonyl (Fe(CO)3*) molecules; (2) an adsorbate assisted movement of iron tricarbonyl on top of the CO adlayer; and (3) the interaction of iron tricarbonyl with CO molecules from the gaseous medium eventually leading to iron adatom removal as Fe(CO)5 gas.

A Multitechnique Study of C2H4 Adsorption on Fe3O4(001).

The adsorption/desorption of ethene (C2H4), also commonly known as ethylene, on Fe3O4(001) was studied under ultrahigh vacuum conditions using temperature-programmed desorption (TPD), scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT)-based computations. To interpret the TPD data, we have employed a new analysis method based on equilibrium thermodynamics. C2H4 adsorbs intact at all coverages and interacts most strongly with surface defects such as antiphase domain boundaries and Fe adatoms. On the regular surface, C2H4 binds atop surface Fe sites up to a coverage of 2 molecules per (√2 × √2)R45° unit cell, with every second Fe occupied. A desorption energy of 0.36 eV is determined by analysis of the TPD spectra at this coverage, which is approximately 0.1-0.2 eV lower than the value calculated by DFT + U with van der Waals corrections. Additional molecules are accommodated in between the Fe rows. These are stabilized by attractive interactions with the molecules adsorbed at Fe sites. The total capacity of the surface for C2H4 adsorption is found to be close to 4 molecules per (√2 × √2)R45° unit cell.

Fe-induced Kondo peak splitting in tip-functionalized scanning tunneling spectroscopy: A first-principles-based simulation

The spin-polarized scanning tunneling microscope (SP-STM) has been employed to enhance its capabilities of detecting the electronic and magnetic properties of organometallic molecules. Using a tip functionalized with a cobaltocene (Cc) molecule, recent SP-STM experiment performed on the Cu-tip/Cc/Fe/Cu(100) composite junction revealed an asymmetric Kondo resonance splitting in the differential conductance (dI/dV) spectrum. However, a systematic theoretical simulation of such system is lacking, and the important roles of the substrate spin-polarization and the Fe adatom still remain to be elucidated. In this work, by combining density functional theory and the hierarchical equations of motion methods, we achieve first-principles-based simulations of the tip control process of the Cu-tip/Cc/Fe/Cu(100) junction. We correctly reproduce the experimental results and demonstrate the influences of the Fe adatom on the spin-polarization of the substrate and on the Kondo resonance splitting in the dI/dV spectra.

Electric-Field-Driven Spin Resonance by On-Surface Exchange Coupling to a Single-Atom Magnet.

Coherent control of individual atomic and molecular spins on surfaces has recently been demonstrated by using electron spin resonance (ESR) in a scanning tunneling microscope (STM). Here, a combined experimental and modeling study of the ESR of a single hydrogenated Ti atom that is exchange-coupled to a Fe adatom positioned 0.6-0.8nm away by means of atom manipulation is presented. Continuous wave and pulsed ESR of the Ti spin show a Rabi rate with two contributions, one from the tip and the other from the Fe, whose spin interactions with Ti are modulated by the radio-frequency electric field. The Fe contribution is comparable to the tip, as revealed by its dominance when the tip is retracted, and tunable using a vector magnetic field. The new ESR scheme allows on-surface individual spins to be addressed and coherently controlled without the need for magnetic interaction with a tip. This study establishes a feasible implementation of spin-based multi-qubit systems on surfaces.

Microscopic theory of spin relaxation of a single Fe adatom coupled to substrate vibrations

Understanding the spin-relaxation mechanism of single adatoms is an essential step towards creating atomic magnetic memory bits or even qubits. Here we present an essentially parameter-free theory by combining \textit{ab-initio} electronic and vibrational properties with the many-body nature of atomic states. Our calculations account for the millisecond spin lifetime measured recently on Fe adatoms on MgO/Ag(100) and reproduce the dependence on the number of decoupling layers and the external magnetic field. We show how the atomic interaction with the environment should be tuned in order to enhance the magnetic stability, and propose a clear fingerprint for experimentally detecting a localized spin-phonon excitation.

Optimizing tip-surface interactions in ESR-STM experiments

Electron-spin resonance carried out with scanning tunneling microscopes (ESR-STM) is a recently developed experimental technique that is attracting enormous interest on account of its potential to carry out single-spin on-surface resonance with subatomic resolution. Here we carry out a theoretical study of the role of tip-adatom interactions and provide guidelines for choosing the experimental parameters in order to optimize spin resonance measurements. We consider the case of the Fe adatom on a MgO surface and its interaction with the spin-polarized STM tip. We address three problems: first, how to optimize the tip-sample distance to cancel the effective magnetic field created by the tip on the surface spin, in order to carry out proper magnetic field sensing. Second, how to reduce the voltage dependence of the surface-spin resonant frequency, in order to minimize tip-induced decoherence due to voltage noise. Third, we propose an experimental protocol to infer the detuning angle between the applied field and the tip magnetization, which plays a crucial role in the modeling of the experimental results.

The influence of adatom diffusion on the formation of skyrmion lattice in sub-monolayer Fe on Ir(111)

Room temperature grown Fe monolayer (ML) on the Ir(111) single crystal substrate has attracted great research interests as nano-skyrmion lattice can form under proper growth conditions. The formation of the nanoscale skyrmion, however, appears to be greatly affected by the diffusion length of the Fe adatoms on the Ir(111) surface. We made this observation by employing spin-polarized scanning tunneling microscopy to study skyrmion formation upon systematically changing the impurity density on the substrate surface prior to Fe deposition. Since the substrate surface impurities serve as pinning centers for Fe adatoms, the eventual size and shape of the Fe islands exhibit a direct correlation with the impurity density, which in turn determines whether skyrmion can be formed. Our observation indicates that skyrmion only forms when the impurity density is below 0.006/nm2, i.e., 12 nm averaged spacing between the neighboring defects. We verify the significance of Fe diffusion length by growing Fe on clean Ir(111) substrate at low temperature of 30 K, where no skyrmion was observed to form. Our findings signify the importance of diffusion of Fe atoms on the Ir(111) substrate, which affects the size, shape and lattice perfection of the Fe islands and thus the formation of skyrmion lattice.

Effects of strong spin-orbit coupling on Shiba states from magnetic adatoms using first-principles theory

Magnetic impurities at surfaces of superconductors can induce bound states referred to as Yu–Shiba–Rusinov states (i.e. Shiba states) within superconducting (SC) gaps. For superconductors with strong spin–orbit coupling (SOC), Shiba states arising from even single magnetic adatoms are too complex to be fully understood using effective models alone because SOC cannot be treated perturbatively and multiple orbitals are strongly mixed with spin projections. Here we investigate Shiba states of single magnetic adatoms at the surface of strongly spin-orbit coupled SC Pb, by solving the fully relativistic Dirac–Bogoliubov–de Gennes equations using multiple scattering Green’s function methods. For Fe and Co adatoms on Pb(110), we show that the Shiba states are better characterized by total angular momentum, J, and its projections on the z axis, m J . As a hallmark of the SOC effect, the Shiba states show a strong dependence of the orientation of the adatom moment. As the orientation of the Fe/Co moment changes, the deepest Shiba states merge at zero energy. This zero-energy state disappears with an additional non-magnetic adatom next to the magnetic adatom, although the other Shiba states unchange. For a Mn adatom on Pb, our Shiba states overall agree with experiments. The characteristics of our Shiba states are also observed with the similar energies and characters in the experiments. The deepest Shiba states that we compute, however, do not appear as close to the Fermi level as the experimental data. It would be interesting to compute the Shiba states with continuously varying vertical distances of the Mn adatom from the surface or with varying the charge state of the adatom, and to calculate the spatial dependence of the spectral density. Our findings will be also useful for understanding of Shiba states for dimers and longer spin chains on the Pb surface considering noncollinear magnetic structures in them.

Systematic study of Mn atoms, artificial dimers, and chains on superconducting Ta(110)

Magnetic adatoms coupled to an $s$-wave superconductor give rise to local bound states, so-called Yu-Shiba-Rusinov states. Focusing on the ultimate goal of tailoring chains of such adatoms into a topologically superconducting phase, we investigate basic building blocks - single Fe and Mn adatoms and Mn dimers on clean superconducting Ta(110) - using scanning tunneling microscopy and spectroscopy. We perform a systematic study of the hybridizations and splittings in dimers, and their dependence on the crystallographic directions and interatomic spacings, in order to identify potentially interesting chain geometries for this novel sample type. Subsequently, we study the spin structure as well as the length dependent Shiba band structure in Mn chains of those geometries using spin-resolved scanning tunneling spectroscopy. All results are compared to the according properties of structurally identical dimers and chains on the previously studied Nb(110), which has almost identical surface structure and electronic properties, but an about three times smaller spin-orbit interaction.

First-principles study of the microstructure evolution of the diamond (110) surface with the adsorption of Fe atoms

Understanding the diamond graphitization mechanism is an essential subject in manufacturing research since it helps elucidate the reason for the material removal. Our work addressed the mechanism of Fe-induced graphitization of diamond (110) surfaces (Dia-(110)-Surf) by first-principles calculations. The results pointed out that Fe atoms adsorbed at hollow sites could acquire the most stable configuration on the Dia-(110)-Surf. Meanwhile, the Fe adatom could change interlayer binding energies of CC bonds of various layered. As the amount of Fe atoms increased, the weakening/enhancement effect of CC bonds tended to be apparent. Interestingly, Fe adatoms not only changed interlayer binding energies of CC nearby but also affected the dissociation direction of the surface microstructure. The weakened CC bonds could provoke the flattening of the sixfold chair ring structure of C atoms. The extension direction of the sixfold chair ring structure changed from horizontal to oblique, resulting in eliminating lateral compressive stress. It might be the origin of the Fe-induced graphitization of Dia-(110)- Surf. Moreover, the migration behaviors of the Fe atom have been studied. It could be inferred that the migration activation energy and movement direction of Fe adatoms were associated with the material removal rate.

Interplay of magnetic states and hyperfine fields of iron dimers on MgO(001)

Individual nuclear spin states can have very long lifetimes and could be useful as qubits. Progress in this direction was achieved on MgO/Ag(001) via detection of the hyperfine interaction (HFI) of Fe, Ti and Cu adatoms using scanning tunneling microscopy. Previously, we systematically quantified from first-principles the HFI for the whole series of 3d transition adatoms (Sc-Cu) deposited on various ultra-thin insulators, establishing the trends of the computed HFI with respect to the filling of the magnetic s- and d-orbitals of the adatoms and on the bonding with the substrate. Here we explore the case of dimers by investigating the correlation between the HFI and the magnetic state of free standing Fe dimers, single Fe adatoms and dimers deposited on a bilayer of MgO(001). We find that the magnitude of the HFI can be controlled by switching the magnetic state of the dimers. For short Fe-Fe distances, the antiferromagnetic state enhances the HFI with respect to that of the ferromagnetic state. By increasing the distance between the magnetic atoms, a transition toward the opposite behavior is observed. Furthermore, we demonstrate the ability to substantially modify the HFI by atomic control of the location of the adatoms on the substrate. Our results establish the limits of applicability of the usual hyperfine hamiltonian and we propose an extension based on multiple scattering processes.

Insight into the graphitization mechanism of the interface between iron and diamond: A DFT study

It is an important topic in the manufacturing research field to understand the mechanisms for the wear of diamond surfaces. The density functional theory (DFT) methods have served as useful tools for studying chemical reaction mechanisms in processing. In this work, we studied the changes in the diamond structure during the interface contact between the iron and diamond. The iron-diamond contact area is simplified to different coverage rates of Fe atom, corresponding to different numbers of adatom. With the different numbers of the Fe adatoms, the interlayer CC bonds have different changes. Below the Fe adatom region, the interlayer CC bonds are strengthened, inhibiting the graphitization. It is noteworthy that the CC bonds became significantly weakened or even broken at the boundary of the interface contact. Moreover, the interface sliding simulation verifies that the graphitization preferentially occurs at the edge of the interface between iron and diamond. The actual cause of graphitization is the synergistic effect of the charge transfer of the FeC bonds and the asymmetric contraction and stretching on the diamond surface. Our work provides a theoretical basis for suppressing excessive diamond tool wear and polishing the diamond surfaces.

Yu-Shiba-Rusinov States in a Superconductor with Topological Z_{2} Bands.

A Yu-Shiba-Rusinov (YSR) state is a localized in-gap state induced by a magnetic impurity in a superconductor. Recent experiments used an STM tip to manipulate the exchange coupling between an Fe adatom and the FeTe_{0.55}Se_{0.45} superconductor possessing a Z_{2} nontrivial band structure with topological surface states. As the tip moves close to the single Fe adatom, the energy of the in-gap state modulates and exhibits a zero-energy crossing followed by an unusual return to zero energy, which cannot be understood by coupling the magnetic impurity to the superconducting topological surface Dirac cone. Here, we numerically and analytically study the YSR states in superconductors with nontrivial Z_{2} bands and show the emergence of the two zero-energy crossings as a function of the exchange coupling between the magnetic impurity and the bulk states. We analyze the role of the topological surface states and compare in-gap states to systems with trivial Z_{2} bands. The spin polarization of the YSR states is further studied for future experimental measurement.

Lieb Lattices Formed by Real Atoms on Ag(111) and Their Lattice Constant-Dependent Electronic Properties

Scanning tunneling microscopy is a powerful tool to build artificial atomic structures that do not exist in nature but possess exotic properties. In this study, we constructed Lieb lattices with different lattice constants by real atoms, i.e., Fe atoms on Ag(111), and probed their electronic properties. We obtain a surprising long-range effective electron wavefunction overlap between Fe adatoms as it exhibits a dependence with the interatomic distance r instead of the theoretically predicted exponential one. Combining control experiments, tight-binding modeling, and Green’s function calculations, we attribute the observed long-range overlap to being enabled by the surface state. Our findings enrich the understanding of the electron wavefunction overlap and provide a convenient platform to design and explore artificial structures and future devices with real atoms.

Molecular dynamics simulation of the growth and diffusion mechanisms of Fe–Cu bimetallic nanoparticles

ABSTRACT In accordance with the molecular dynamic simulation and nudged elastic band method, the surface diffusion and growth of Fe–Cu nanoparticles were studied, respectively, using Large-scale Atomic/Molecular Massively Parallel Simulator code. Results showed that a single Cu adatom diffused on the surface of the Fe substrate mainly via the hopping mechanism and nearly did not exchange with the substrate atoms. In the Cu substrate, when interfacet diffusion of a Fe adatom on the surface was activated, the system energy evidently decreased after the exchange mechanism was chosen. At low temperatures, the metastable core–shell structure of FeshellCucore nanoparticles was obtained by simulating the deposition of Fe on Cu substrate. For the growth of Cu on Fe substrate, FecoreCushell nanoparticles could be formed and they gradually evolved into Wulff-like structures with depositing Cu atoms. The Monte Carlo calculation further showed that the stable configuration of Fe–Cu nanoparticles is FecoreCushell when the concentration of Cu atoms is small. With the increase of Cu atomic ratio (enough to cover the surface), the quasi-Janus was the stable structure in Fe–Cu nanoparticles.

Moiré Tuning of Spin Excitations: Individual Fe Atoms on MoS_{2}/Au(111).

Magnetic adatoms on properly designed surfaces constitute exquisite systems for addressing, controlling, and manipulating single quantum spins. Here, we show that monolayers of MoS_{2} on a Au(111) surface provide a versatile platform for controllably tuning the coupling between adatom spins and substrate electrons. Even for equivalent adsorption sites with respect to the atomic MoS_{2} lattice, we observe that Fe adatoms exhibit behaviors ranging from pure spin excitations, characteristic of negligible exchange and dominant single-ion anisotropy, to a fully developed Kondo resonance, indicating strong exchange and negligible single-ion anisotropy. This tunability emerges from a moiré structure of MoS_{2} on Au(111) in conjunction with pronounced many-body renormalizations. We also find striking spectral variations in the immediate vicinity of the Fe atoms, which we explain by quantum interference reflecting the formation of Fe-S hybrid states despite the nominally inert nature of the substrate. Our work establishes monolayer MoS_{2} as a tuning layer for adjusting the quantum spin properties over an extraordinarily broad parameter range. The considerable variability can be exploited for quantum spin manipulations.

Robust topological state against magnetic impurities observed in the superconductor PbTaSe2

Magnetic impurities deposited on topological superconductor candidate PbTaSe2 can introduce a non-splitting zero-energy state inside the superconducting gap, which has been proposed as a field-free platform for topological zero modes. However, it is still unclear how robust the topological state in PbTaSe2 is against magnetic impurities, which is related to the topological nature of the zero-energy state as well as its potential for quantum computation. In this work, we use scanning tunneling microscopy (STM) to study the topological surface state in the normal state of PbTaSe2 under the perturbation of magnetic impurities. We visualize the quasi-particle interference (QPI) arising from the topological surface state. We then deposit Fe impurities on the surface to form atomic Fe adatoms. We find that each Fe adatom sits at a unique interstitial position on the surface and features a local state at high energies, both of which are consistent with our first-principles calculation that further reveals its large magnetic moment. Our systematic Fe deposition and subsequent measurements show that the arc-like QPI pattern at the Fermi energy is robust with up to 3% Fe coverage where the atomic nature of Fe adatoms still holds. Our results provide evidence that the topological surface state at the Fermi energy in PbTaSe2 is robust against dilute magnetic impurities.

Correlation of Yu-Shiba-Rusinov States and Kondo Resonances in Artificial Spin Arrays on an s-Wave Superconductor.

Mutually interacting magnetic atoms coupled to a superconductor have gained enormous interest due to their potential for the realization of topological superconductivity. Individual magnetic impurities produce states within the superconducting energy gap known as Yu–Shiba–Rusinov (YSR) states. Here, using the tip of a scanning tunneling microscope, we artificially craft spin arrays consisting of an Fe adatom interacting with an assembly of interstitial Fe atoms (IFA) on a superconducting oxygen-reconstructed Ta(100) surface and show that the magnetic interaction between the adatom and the IFA assembly can be tuned by adjusting the number of IFAs in the assembly. The YSR state experiences a characteristic crossover in its energetic position and particle–hole spectral weight asymmetry when the Kondo resonance shows spectral depletion around the Fermi energy. By the help of slave-boson mean-field theory (SBMFT) and numerical renormalization group (NRG) calculations we associate the crossover with the transition from decoupled Kondo singlets to an antiferromagnetic ground state of the Fe adatom spin and the IFA assembly effective spin.

Towards advanced complex quantum materials for spin-related applications and photo-induced heterogeneous catalysis: The case of (Fen)@g-CN1 (n = 2,3) and (Mn)@(g-CN1)2

Perspective heterostructures based on Fe and Mn adatoms on 2D g-C3N4 films of different morphology were designed and investigated by means of DFT GGA/PBE and GGA/HSE levels of theory. Spontaneous spin polarization of g-C3N4 and a variety of electronic properties were theoretically investigated. It was found that GGA HSE DFT potential is suitable to describe the main properties of g-C3N4-based heterostructures with transition metal adatoms. It was revealed that (Mn)@(g-CN1)2 heterostructure is a half-metal with 0.5 eV band gap in α-channel. (Fen)@g-CN1, n = 2,3) demonstrate different semiconducting properties which are determined by structure and number of Fe adatoms in the unit cells. The presence of several independent centers of Fe forming polyatomic clusters was stated as one of the interests in catalysis. It was found that all considered heterostructures may serve as perspective quantum materials in different spin-related applications.