Reversible Single Spin Control of Individual Magnetic Molecule by Hydrogen Atom Adsorption
Liwei Liu, Kai Yang, Yuhang Jiang, Boqun Song, Wende Xiao, Linfei Li, Haitao Zhou, Yeliang Wang, Shixuan Du, Min Ouyang, Werner A. Hofer, Antonio H. Castro Neto, Hong-Jun Gao
The reversible control of a single spin of an atom or a molecule is of great interest in Kondo physics and a potential application in spin based electronics.Here we demonstrate that the Kondo resonance of manganese phthalocyanine molecules on an Au(111) substrate have been reversibly switched off and on via a robust route through attachment and detachment of single hydrogen atom to the magnetic core of the molecule. As further revealed by density functional theory calculations, even though the total number of electrons of the Mn ion remains almost the same in the process, gaining one single hydrogen atom leads to redistribution of charges within 3d orbitals with a reduction of the molecular spin state from S = 3/2 to S = 1 that directly contributes to the Kondo resonance disappearance. This process is reversed by a local voltage pulse or thermal annealing to desorb the hydrogen atom.
In order to realize applications of hydrogen-adsorbed graphene, a main issue is how to control hydrogen adsorption/desorption at room temperature. In this study, we demonstrate the possibility to tune hydrogen adsorption on graphene by applying a gate voltage. The influence of the gate voltage on graphene and its hydrogen adsorption properties was investigated by electrical transport measurements, scanning tunneling microscopy, and density functional theory calculations. We show that more hydrogen adsorbs on graphene with negative gate voltage (p-type doping), compared to that without gate vol…
By means of ab initio calculations, we have investigated the effect of H adsorption in the structural, electronic and magnetic properties of ultrathin Co films on Ru(0001). Our calculations predict that H occupies hollow sites preserving the two-dimensional 3-fold symmetry. The formation of a complete H overlayer leads to a very stable surface with strong H-Co bonds. H tends to suppress surface features, in particular, the enhancement of the magnetic moments of the bare film. The H-induced effects are mostly confined to the Co atoms bonded to H, independent of the H coverage or of the thicknes…
Graphene functionalization by hydrogen and fluorine has been proposed as a route to modulate its reactivity and electronic properties. However, until now, proposed systems present degradation and limited hydrogen adsorption capacity. In this study, combining first-principles calculations based on density functional theory (DFT) and reactive molecular dynamics, we analyze the tuning of hydrogen adsorption and electronic properties in fluorinated and hydrogenated monolayer graphenes. Our results indicate that fluorine adsorption promotes stronger carbon$-$hydrogen bonds. By changing the concentr…
The ability of atomic hydrogen to chemisorb on graphene makes the latter a promising material for hydrogen storage. Based on scanning tunneling microscopy techniques, we report on site-selective adsorption of atomic hydrogen on convexly curved regions of monolayer graphene grown on SiC(0001). This system exhibits an intrinsic curvature owing to the interaction with the substrate. We show that at low coverage hydrogen is found on convex areas of the graphene lattice. No hydrogen is detected on concave regions. These findings are in agreement with theoretical models which suggest that both bindi…
We have carried out first-principles calculations of Be(0001) thin films to study the oscillatory quantum size effects exhibited in the surface energy, work function, and binding energy of the atomic hydrogen monolayer adsorption. The prominent enhancement of the surface density of states at the Fermi level makes Be(0001) thin films more metallic compared to the crystalline Be. As a result, the calculated energetics of Be films and the properties of atomic H adsorption onto Be(0001) surface are featured by a quantum oscillatory behavior. Furthermore, The prominent change in the Be(0001) surfac…
The adsorption of hydrogen on the polar Zn-ended ZnO(0001) surface has been investigated by density functional {\it ab-initio} calculations. An on top H(1x1) ordered overlayer with genuine H-Zn chemical bonds is shown to be energetically favorable. The H covered surface is metallic and spin-polarized, with a noticeable magnetic moment at the surface region. Lower hydrogen coverages lead to strengthening of the H-Zn bonds, corrugation of the surface layer and to an insulating surface. Our results explain experimental observations of hydrogen adsorption on this surface, and not only predict a me…
We present a first-principles study of the atomic hydrogen adsorption onto the Be(10\={1}0) thin film. There are two types of Be(10\={1}0) surfaces according to the interlayer spacing between the surface and its nearest-neighbor layer. We show that the H adsorption features on these two kinds of surfaces are remarkably different. The work function, averaged electrostatic potential, and the local charge density consistently show that the charge is transferred from H to Be for L-type (see the text below) surfaces, while the transfer process is inverted for S-type surfaces.
Hydrogen adsorption on graphene in commensurate periodic arrangements leads to bandgap opening at the Dirac point and the emergence of dispersionless midgap bands. We study these bandgap effects and their dependence on periodicity for a single hydrogen adsorbate on periodic graphene supercells using spin-polarized density-functional theory calculations. Our results show that for certain periodicities, marked by a scale factor of three, the bandgap is suppressed to a great extent, and has a special level structure around the neutrality point. We present explanations for the origin of the change…
We have performed first-principles studies on adsorption patterns of hydrogen adatoms on uniaxially strained graphene. Our simulation reveals that the adsorption energy of adatoms are sensitive to the strain. Hydrogen adatoms on zigzag strained graphene tend to form a chain-like adsorption patterns perpendicular to the strain direction, but those under armchair strain cannot form any long-range chain pattern. We explain our results in terms of a tight-binding model and the electronic structure of strained graphene. These anisotropic adsorption behaviors under uniaxial strain suggest methods fo…
Grand Canonical Monte Carlo (GCMC) simulations are performed to study hydrogen physisorption in different nano carbon porous materials made up of different substructures including carbon nanotubes (CNT), graphene sheets and C60. Hydrogen weight percentage (wt%) at different temperatures with pressure ranging from 1 to 20MPa are predicted. Fugacity and quantum effects on hydrogen adsorption are investigated. Different structural dimensions including the sizes of the substructures and spacing between the substructures are used to study the geometrical effects on hydrogen storage capacity in carb…
We use the non-interacting tight-binding model to study the effect of isolated hydrogen adsorbates on the quasiparticle spectra of single-layer graphene. Using the Green's function approach, we obtain analytic expressions for the local density of states and the spectral function of hydrogen-doped graphene, which are also numerically evaluated and plotted. Our results are relevant for the interpretation of scanning tunneling microscopy and angle-resolved photoemission spectroscopy data of functionalized graphene.
The effect of hydrogen adsorption on the magnetic properties of an Fe$_3$ cluster immersed in a Cu(111) surface has been calculated using densifty functional theory and the results used to parametrize an Alexander-Anderson model which takes into account the interaction of d-electrons with itinerant electrons. A number of adatom configurations containing one to seven H-atoms were analyzed. The sequential addition of hydrogen atoms is found to monotonically reduce the total magnetic moment of the cluster with the effect being strongest when the H-atoms sit at low coordinated sites. Decomposition…
First-principles density functional theory (DFT) is employed to investigate the interactions of CO2 gas molecules with pristine and lithium-functionalized germanene. It is discovered that although a single CO2 molecule is weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy is found by utilizing Li-functionalized germanene as the adsorbent. However, the moderate adsorption energy at high CO2 coverage predicts an easy release step. More excitingly, the structure of Li-functionalized germanene can be fully recovered after removal of CO2 gas molecules. Our …
We have carried out first-principles calculation of Mg(0001) free-standing thin films to study the oscillatory quantum size effect exhibited in the surface energy, work function, interlayer relaxation, and adsorption energy of the atomic hydrogen adsorbate. The quantum well states have been shown. The calculated energetics and interlayer relaxation of clean and H-adsorbed Mg films are clearly featured by quantum oscillations as a function of the thickness of the film, with oscillation period of about 8 monolayers, consistent with recent experiments. The calculated quantum size effect in H adso…
Graphone is a half-hydrogenated graphene. The structure of graphone is illustrated as trigonal adsorption of hydrogen atoms on graphene at first. However, we found the trigonal adsorption is unstable. We present an illustration in detail to explain how a trigonal adsorption geometry evolves into a rectangular adsorption geometry. We check the change of magnetism during the evolution of geometry by evaluating the spin polarization of the intermediate geometries. We prove and clarify that the rectangular adsorption of hydrogen atoms on graphene is the most stable geometry of graphone and graphon…
The graphane with chemically bonded alkali metals (Li, Na, K) was considered as potential material for hydrogen storage. The ab initio calculations show that such material can adsorb as many as 4 hydrogen molecules per Li, Na and K metal atoms. These values correspond to 12.20 wt%, 10.33 wt% and 8.56 wt% of hydrogen, respectively and exceed the DOE requirements. The thermodynamic analysis shows that Li-graphane complex is the most promising for hydrogen storage with ability to adsorb 3 hydrogen molecules per metal atom at 300 K and pressure in the range from 5 to 250 atm.
Hydrogen adsorption on graphene can be increased by functionalization with Ti. This requires dispersing Ti islands on graphene as small and dense as possible, in order to increase the number of hydrogen adsorption sites per Ti atom. In this report, we investigate the morphology of Ti on nanocrystalline graphene and its hydrogen adsorption by scanning tunneling microscopy and thermal desorption spectroscopy, and compare the results with equivalent measurements on single-crystalline graphene. Nanocrystalline graphene consists of extremely small crystal grains of < 5 nm size. Ti atoms preferentia…
The absorption energy of atomic hydrogen at rotated graphene bilayers is studied using ab initio methods based on the density functional theory including van der Waals interactions. We find that, due to the surface corrugation induced by the underneath rotated layer and the perturbation of the electronic density of states near the Fermi energy, the atoms with an almost AA stacking are the preferential ones for hydrogen chemisorption. The adsorption energy difference between different atoms can be as large as 80 meV. In addition, we find that, due to the logarithmic van Hove singularities in th…
The interaction of atomic hydrogen with a single layer of hexagonal boron nitride on rhodium leads to a removal of the h-BN surface corrugation. The process is reversible as the hydrogen may be expelled by annealing to about 500 K whereupon the texture on the nanometer scale is restored. This effect is traced back to hydrogen intercalation. It is expected to have implications for applications, like the storage of hydrogen, the peeling of sp2-hybridized layers from solid substrates or the control of the wetting angle, to name a few.
We propose a multi-layer graphene-based device in which storage and release of atomic hydrogen is obtained by exploiting and controlling the corrugation of the layers. The proposal is based on density-functional simulations of hydrogen chemisorption on graphene with superimposed corrugation. We report a tunability of the binding energies of more than 2 eV by changing the sheet out-of-plane deformation up to \pm 0.2 Å, the convex regions allocating the energetically favored hydrogen binding sites. We discuss an optimized process of curvature inversion that can lead to efficient and fast hydroge…
The adsorption of hydrogen on Au nanoparticles (NPs) of size of the order of 10 nm has been investigated by use of localised surface plasmon resonances (LSPR) in the NPs. The samples, formed by Au NPs obtained by oblique angle deposition on glass substrates, display a strong optical dichroism due to two different plasmon resonances dependent on the polarisation of light. This ensured the use of Transmittance Anisotropy Spectroscopy, a sensitive derivative optical technique, which permitted one to measure shifts of the LSPR as small as 0.02 nm upon H adsorption, which is not accessible by conve…
Graphene is the extreme material for molecular sensory and hydrogen storage applications because of its two-dimensional geometry and unique structure-property relationship. In this Letter, hydrogenation of graphene is discussed in the extent of intercoupling between mechanical deformation and electronic configuration. Our first principles calculation reveals that the atomic structures, binding energies, mechanical and electronic properties of graphene are significantly modified by the hydrogenation and applied strain. Under an in-plane strain of 10 %, the binding energies of hydrogen on graphe…
The creation of magnetism on non-magnetic semiconductor surfaces is of importance for the realization of spintronics devices. Especially, the coupling of electron spins within quantum nanostructures can be utilized for nanomagnetism applications. Here, we demonstrate, based on first-principles density-functional theory calculations, that the adsorption of H atoms on the Si(111)-(7$\times$7) surface induces the spin polarization of surrounding Si dangling bonds (DBs) and their spin orderings. It is revealed that the H adsorption on a rest-atom site exhibits a Jahn-Teller-like distortion that ac…
We report the experimental observation of sublattice-resolved resonant scattering in bilayer graphene by performing simultaneous cryogenic atomic hydrogen doping and electron transport measurements in ultrahigh vacuum. This allows us to monitor the hydrogen adsorption on the different sublattices of bilayer graphene without atomic-scale microscopy. Specifically, we detect two distinct resonant scattering peaks in the gate-dependent resistance, which evolve as a function of atomic hydrogen dosage. Theoretical calculations show that one of the peaks originates from resonant scattering by hydroge…
Pristine graphene is not suitable for hydrogen storage at ambient conditions since it binds the hydrogen molecules only by van der Waals interactions. However, the adsorption energy of the hydrogen molecules can be improved by doping or decorating metal atoms on the graphene monolayer. The doping and decoration processes are challenging due to the oxygen interference in hydrogen adsorption and the clustering issue of metal atoms. To improve the hydrogen adsorption energy in pristine graphene, we have explored the hydrogen storage capabilities of graphene monolayer in the presence of compressiv…
The OH-terminated self-assembled monolayers, as protein-resistant surfaces, have significant potential in biocompatible implant devices, which can avoid or reduce adverse reactions caused by protein adhesion to biomaterial surfaces, such as thrombosis, immune response and inflammation. Here, molecular dynamics simulations were performed to evaluate the degree of protein adsorption on the self-assembled monolayer terminated with two hydrophilic OH groups ((OH)2-SAM) at the packing densities (Σ) of 4.5 nm-2 and 6.5 nm-2, respectively. The results show that the (OH)2-SAM itself can significantly …
The adsorption behaviour of hazardous gas molecules, namely nitrogen dioxide (NO$_2$) and ammonia (NH$_3$), on phosphorene nanosheet (PNS) was explored by means of ab initio technique. To improve the structural solidity of pristine PNS, we have introduced the passivation of hydrogen and fluorine at the terminated edge. The structural solidity of both hydrogen and fluorine passivated PNS is verified in terms of formation energy. The main objective of this research work is to probe NO$_2$ and NH$_3$ gases using PNS as a base sensing material. The adsorption of various preferential adsorption sit…
For graphene to be used in semiconductor applications, a wide energy gap of at least 0.5 eV at the Dirac energy must be opened without the introduction of atomic defects. However, such a wide energy gap has not been realized in graphene, except in the cases of narrow, chemically terminated graphene nanostructures with inevitable edge defects. Here, we demonstrated that a wide energy gap of 0.74 eV, which is larger than that of germanium, could be opened in uniform monolayer graphene without the introduction of atomic defects into graphene. The wide energy gap was opened through the adsorption …
Using helium-3 atom scattering, we have studied the adsorption kinetics, the structure and the diffusional dynamics of atomic hydrogen on the surface of a graphene monolayer on Ni(111). Diffraction measurements reveal a 4$^\circ$ rotated rectangular hydrogen overstructure. Hydrogen adsorption and desorption exhibit activation barriers of $E_a=(89\pm7)\,$meV and $E_d=(1.8\pm0.2)\,$eV, respectively. Helium-3 spin-echo measurements showed no decay of the spatial correlation function (or intermediate scattering function) within the time range of the spectrometer. Hence, we are able to set lower li…
Investigation of phosphate species adsorption/desorption processes was performed on Ag(100) and Ag(111) electrodes in H$_{3}$PO$_{4}$, KH$_{2}$PO$_{4}$ and K$_{3}$PO$_{4}$ solutions by Current-Potential ($j-V$) profiles and Electrochemical Impedance Spectroscopy ($EIS$). We used the equivalent circuit method to fit the impedance spectra. Different electrical equivalent circuits ($EECs$) were employed depending on the potential region that was analyzed. For potentials more negative than the onset of the hydrogen evolution reaction ($her$), a charge transfer resistance (R$_{ct}$) in parallel to …
The Dzyaloshinskii-Moriya interaction (DMI) has drawn great attention as it stabilizes magnetic chirality, with important implications in fundamental and applied research. This antisymmetric exchange interaction is induced by the broken inversion symmetry at interfaces or in non-centrosymmetric lattices. Significant interfacial DMI was found often at magnetic / heavy-metal interfaces with large spin-orbit coupling. Recent studies have shown promise of induced DMI at interfaces involving light elements such as carbon (graphene) or oxygen. Here we report direct observation of induced DMI by chem…
We calculate the electronic structure and magnetic properties of hydrogenated graphite surfaces using van der Waals density functional theory (DFT) and model Hamiltonians. We find, as previously reported, that the interaction between hydrogen atoms on graphene favors adsorption on different sublattices along with an antiferromagnetic coupling of the induced magnetic moments. On the contrary, when hydrogenation takes place on the surface of graphene multilayers or graphite (Bernal stacking), the interaction between hydrogen atoms competes with the different adsorption energies of the two sublat…
Based on DFT+U and Berry curvature calculations, we study the electronic structures and topological properties of 3d transition metal (TM) atom (from Ti to Co) adsorbed germanene (TM-germanene). We find that valley-polarized anomalous hall effect (VAHE) can be realized in germanene by adsorbing Cr, Mn, or Co atom on its surface. A finite valley hall voltage can be easily detected in its nanoribbon, which is important for valleytronics devices. Moreover, different valley-polarized current and even reversible valley Hall voltage can be archived by shifting the Fermi energy of the systems. Such v…
Graphene - a monolayer of carbon atoms densely packed into a hexagonal lattice - has one of the strongest possible atomic bonds and can be viewed as a robust atomic-scale scaffold, to which other chemical species can be attached without destroying it. This notion of graphene as a giant flat molecule that can be altered chemically is supported by the observation of so-called graphene oxide, that is graphene densely covered with hydroxyl and other groups. Unfortunately, graphene oxide is strongly disordered, poorly conductive and difficult to reduce to the original state. Nevertheless, one can i…
Both experimental and theoretical studies of the magnetic properties of micrographite and nanographite indicate a crucial role of the partial oxidation of graphitic zigzag edges in ferromagnetism. In contrast to total and partial hydrogenation, the oxidation of half of the carbon atoms on the graphite edges transforms the antiferromagnetic exchange interaction between graphite planes and over graphite ribbons to the ferromagnetic interaction. The stability of the ferromagnetism is discussed.
