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Craters have been observed upon irradiation by single ion impacts of Ar monomer and Ar dimer ions with 35 keV/atom in monolayer graphene on copper at a fluence of 1 × 1012 atoms/cm2. The observed craters at the ion impacts are in the underlying copper substrate, which pull down the graphene layer conformally towards them, introducing disorder into graphene. The number density of craters per atom produced by Ar-monomers is higher than that of Ar-dimer ions. In the ion impact region, disorder is high, and graphene is metallic in both Ar-monomer and dimer irradiation. In the ion impact region of dimer irradiated graphene, local density of states is higher and there is a shift in Dirac point position by +0.07 eV and a bandgap opening of 0.25 eV in the ordered region ∼15 nm away from the ion impact. Microscopic ripples in graphene are not observed in the case of monomer irradiation while they are present in the case of dimer irradiation with a reduced wavelength. Isotropic compressive strain is introduced by the ion impacts and it is larger for Ar-dimer irradiation. The combined effects of compressive strain along with breaking the equivalence between A and B sublattice of graphene is attributed to the opening of the band gap in graphene.

We employ the first-principles calculation with non-equilibrium Green's function method to comprehensively investigate the crucial role of interfacial geometry in spin transport properties of Co/1,4-benzenediamine (BDA)/Co single-molecule magnetic junctions (SMMJs). Two bonding mechanisms are proposed for the hard-hard Co-N coupling: (1) the covalent bonding between the H-dissociated amine linker and spin-polarized Co apex atoms and (2) the dative interaction between the H-non-dissociated (denoted by +H) amine linker and Co apex atoms. The former covalent contact dominates the π-resonance interfacial spin selection that can be well preserved in H-dissociated cases regardless of the choice of top, bridge, and hollow contact sites. From our detailed analyses of spin-polarized transmission spectra, local density of states, and molecular density of states, the underlying mechanism is that the strong hybridization between Co-d, N-p y , and the π-orbital of the phenyl ring in dissociated cases renders the 2-fold HOMO (4-fold LUMO) of the central molecule closer to the Fermi energy. In contrast, the enlarged Co-N bond length of the latter dative contact in the H-non-dissociated case not only destroys the spinterface coupling but also blocks the spin injection. This theoretical work may provide vital and practical insights to illustrate the spin transport property in real amine-ended SMMJs since the contact geometries and interfacial bond mechanisms remain unclear during the breaking junction technique.

We examine the transport properties of multi-channels of a porphyrin phenylacetylene (PPA) molecule by changing gate and source voltages at its two terminals. Density functional theory (DFT) within the non-equilibrium Green's function framework (NEGF) is employed to calculate the four probe PPA device by connecting with four Au electrodes using S linkages. Two gate voltages are chosen as 0.6 V (denoted as PPA-0.6) and 1.0 V (denoted as PPA-1.0), respectively. At each certain gate voltage, source voltages are applied in the range of 0.0 V to 1.0 V at a step of 0.2 V. It is found that the magnitude of the gate voltage plays a significant role in the whole transport property. No matter in PPA-0.6 or in PPA-1.0, evident NDR behavior is observed for lead currents. Moreover, a smaller gate voltage could induce a more prominent NDR effect. On the other hand, the relative magnitude of the gate voltage and the source voltage determines the current directions of the gate and source leads. Furthermore, input/output current switches can be achieved for the gate lead at the critical voltage of Vgate = Vsource. These interesting transport characteristics are further analyzed from the transmission spectra and the local density of states (LDOS). This presentation provides a clue for exploring novel functional nano-electronic molecular devices based on PPA by tuning gate voltages and source voltages as well as changing lead-to-lead channels.

Electronic interface properties and the initial growth of hexa-peri-hexabenzocoronene with a borazine core (BN-HBC) on Au(111) have been studied by using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM). A weak, but non-negligible, interaction between BN-HBC and Au(111) was found at the interface. Both hexa-peri-hexabenzocoronene (HBC) and BN-HBC molecules form well-defined monolayers. The different contrast in STM images of HBC and BN-HBC at different tunneling voltages with submolecular resolution can be ascribed to differences in the local density of states (LDOS). At positive and negative tunneling voltages, STM images reproduce the distribution of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) as determined by density functional theory (DFT) calculations very well.

Using the tight-binding approach, we investigate the electronic and magneto-optical properties of bilayer phosphorene quantum dots (BLPQDs) in the presence of perpendicular electric and magnetic fields. The magneto-energy spectra of the BLPQDs exhibit Aharonov–Bohm oscillations. The period and the amplitude of the oscillation decrease with the size of the BLPQDs. An oscillatory behavior of the local density of states (LDOS) versus the magnetic field is observed, as well as the appearance of the spatial Aharonov–Bohm oscillations in the LDOS. In the absence of the electric field, there exists an s-fold degeneracy (s absolutely flat bands at exactly zero energy) arising from the edge-mode states, where s is the smaller value between M and N, where M and N are the number of phosphorus atoms along the x and y axis, respectively, in a rectangular BLBPQD. The absorption spectra of the BLPQDs are obtained for both in-plane and out-of-plane polarizations. Compared with the absorption spectra of graphene dots, the absorption of an out-of-plane polarization of the incident light is high compared to that of in-plane polarizations. On the other hand, the absorption spectra due to in-plane polarizations are almost the same in the case of graphene, whereas they are considerably different in BLBPQDs. Importantly, the appearance of several sharp and high absorption peaks in the near-infrared (NIR) range dictates the BLBPQDs for application and development of bioimaging, biomedicine and drug delivery technology. More importantly, both the location and intensity of these NIR peaks depend characteristically on the orientation of the polarization of the incident light, which can be desirably tuned by the simultaneous engineering of magnetic and electric fields. Such unique advantage of the anisotropic optical feature enables a new degree of freedom for achieving novel polarization-dependent photonic devices. The dual magnetic and electric field tunable optical and electrical features of the BLPQDs are expected to have important consequences for the development of multifunctional magneto-optoelectronic devices and provide insight into the applicability of quantum photopic technologies based on BLBPQDs.

International audience; Rock-salt lead selenide nanocrystals can be used as building blocks for large scale square superlattices via two-dimensional assembly of nanocrystals at a liquid-air interface followed by oriented attachment. Here we report Scanning Tunneling Spectroscopy (STS) measurements of the local density of states of an atomically coherent superlattice with square geometry made from PbSe nanocrystals. Controlled annealing of the sample permits the imaging of a clean structure and to reproducibly probe the band gap and the valence hole and conduction electron states. The measured band gap and peak positions are compared to the results of optical spectroscopy and atomistic tight-binding calculations of the square superlattice band Electronic properties of atomically coherent square PbSe nanocrystal superlattice resolved by Scanning Tunne structure. In spite of the crystalline connections between nanocrystals that induce significant electronic couplings, the electronic structure of the superlattices remains very strongly influenced by the effects of disorder and variability.

Fluorescent molecules are highly susceptible to their local environment. Thus, a fluorescent molecule near a plasmonic nanoparticle can experience changes in local electric field and local density of states that reshape its intrinsic emission spectrum. By avoiding ensemble averaging while simultaneously measuring the super-resolved position of the fluorophore and its emission spectrum, single-molecule hyperspectral imaging is uniquely suited to differentiate changes in the spectrum from heterogeneous ensemble effects. Thus, we uncover for the first time single-molecule fluorescence emission spectrum reshaping upon near-field coupling to individual gold nanoparticles using hyperspectral super-resolution fluorescence imaging, and we resolve this spectral reshaping as a function of the nanoparticle/dye spectral overlap and separation distance. We find that dyes bluer than the plasmon resonance maximum are red-shifted and redder dyes are blue-shifted. The primary vibronic peak transition probabilities shift to favor secondary vibronic peaks, leading to effective emission maxima shifts in excess of 50 nm, and we understand these light-matter interactions by combining super-resolution hyperspectral imaging and full-field electromagnetic simulations.

Interface engineering of CdS/CZTS(Se) is an important aspect of improving the performance of buffer/absorber heterojunction combination. It has been demonstrated that the crossover phenomenon due to the interface recombination can be drastically eliminated by interface modification. Therefore, in-depth studies across the CdS/CZTS(Se) junction properties, as well as effective optimization processes, are very crucial for achieving high-efficiency CZTSSe solar cells. Here, we present a comprehensive study on the effects of soft-baking (SB) temperature on the junction properties and the corresponding optoelectronic and interface-structural properties. Based on in-depth photoemission studies corroborated with structural and composition analysis, we concluded that interdiffusion and intermixing of CZTSSe and CdS phases occurred on the Cu-poor surface of CZTSSe at elevated SB temperatures, and the interface dipole moments induced by electrostatic potential fluctuation were thus significantly eliminated. In contrast, with low SB temperature, the CdS/CZTSSe heterojunction revealed very sharp interface with very short interdiffusion, forming interface dipole moments and drastically deteriorating device performance. These post thermal treatments also significantly suppress defect energy level of interface measured by admittance spectroscopy from 294 to 109 meV due to CdS/CZTSSe interdiffusion. Meanwhile, the interdiffusion effects on the shift of valence band maximum, conduction band minimum and band offset across the heterojunction of thermally treated CdS/CZTSSe interface are spatially resolved at the atomic scale by measuring the local density of states with cross-sectional scanning tunneling microscopy and spectroscopy. A significant enhancement in the power conversion efficiency from 4.88% to 8.48% is achieved by a facile interface engineering process allowing a sufficient intermixing of CdS/Cd and CZTSSe/Se phases without detrimental recombination centers.

The photoluminescence quantum yield characterizes the performance of emitters for applications in optical devices, as reporters or probes in material and analytical sciences, and for sensing applications. Quantum yield measurements are challenging for luminescent molecules and nanocrystals immobilized in thin films for many sensor applications, particularly if spatially resolved quantitative luminescence information is desired. We show here that a Drexhage-type experiment, where a silver-coated millimeter-sized sphere is used to modify the local density of states, can provide an elegant approach to counter this challenge. As a representative example of the potential of this method, we measure the pH-dependent photoluminescence quantum yield of fluorescein isothiocyanate bound to a thin mesoporous silica film. The results were compared with those of the studies on the pH dependence of the same dye in solution. We found that our approach can link single fluorophore studies to ensemble measurements and pave ...

Synthesis of atomically pure carbon nanotubes (CNT) is difficult. Often, defects form in the structures consisting of carbon rings of non-uniform size and shape. Employing density functional theory combined with a Greens function scattering approach; we investigate the electronic properties of defective CNTs. We use the sculpturene method to form CNTs with a range of defect types, consisting of four-, five-, seven-, eight-, and ten-atom rings. We find that these defects have a non-trivial effect on the transport, often leading to decreased conductance, but also effecting the band-gap (Eg). We also plot the local density of states around the Fermi energy for a range of systems and generally find that higher levels of disorder cause a greater degree of localisation, which helps to explain the electronic properties.

Among the recent achievements of sodium-ion battery (SIB) electrode materials, hybridization of two-dimensional (2D) materials is one of the most interesting appointments. In this work, we propose to use the 2D hybrid composites of SnS2 with graphene or graphene oxide (GO) layers as the SIB anode, based on the first-principles calculations of their atomic structures, sodium intercalation energetics, and electronic properties. The calculations reveal that a graphene or GO film can effectively support not only the stable formation of a heterointerface with the SnS2 layer but also the easy intercalation of a sodium atom with low migration energy and acceptable low volume change. The electronic charge-density differences and the local density of states indicate that the electrons are transferred from the graphene or GO layer to the SnS2 layer, facilitating the formation of a heterointerface and improving the electronic conductance of the semiconducting SnS2 layer. These 2D hybrid composites of SnS2/G or GO ar...

Silicon (Si) donors in GaAs have been the topic of extensive studies since Si is the most common and well understood n-type dopant in III-V semiconductor devices and substrates. The indirect bandgap of AlAs compared to the direct one of GaAs leads to interesting effects when introducing Si dopants. Here we present a study of cross-sectional scanning tunneling microscopy (X-STM) and density functional theory (DFT) calculations to study Si donors in AlAs at the atomic scale. Based on their crystal symmetry and contrast strengths, we identify Si donors up to four layers below the (110) surface of AlAs. Interestingly, their short-range local density of states (LDOS) is very similar to Si atoms in the (110) surface of GaAs. Additionally we show high-resolution images of Si donors in all these layers. For empty state imaging, the experimental and simulated STM images based on DFT show excellent agreement for Si donor up to two layers below the surface.

In previous reports, experimental studies have shown that both thermal stability and strength can be controlled by grain boundary (GB) segregation. In this study, we investigate the segregation behavior of solute (Ti, Ag and Ta) atoms to low/high-angle symmetric tilt grain boundaries (STGBs) of W using density functional theory (DFT) calculations and supported by TEM experiments. We found no segregation preference for Ti or Ta at low-angle STGBs; however, they exhibit a slight segregation tendency to the core of high-angle STGBs. In contrast, Ag is more prone to segregate in and all around the GB plane. We estimated the mechanical and electronic contributions to solution energy and found that the electronic contribution is dominant. Furthermore, the role of d − valence electrons of solute and W atoms, was analyzed using the local density of states (PDOS). We found that substantial d − valence electrons hybridization in the case of Ta plays an important role in stabilizing W-Ta bonds, while the anisotropic nature of W-Ti bond contributes to stabilize surrounding W atoms. Charge transfer analysis revealed that Ti and Ta lose electrons to W atoms. Contrary to the electronegativity rule, Ag atoms gain charge from neighboring W atoms and excellent s − s hybridization may explain the increased GB segregation of Ag atoms.

We propose a mechanism to substantially rectify radiative heat flow by having one side of the thermal diode offering a large contrast in the local density of electromagnetic states, while the opposite side serving as a narrow bandpass filter that limits the transport to a desired spectral range. To demonstrate, we realize such a scenario by matching thin films of metal-to-insulator transition materials and polar dielectrics in the near field. By leveraging the distinct scaling behaviors of the local density of states with film thickness for metals and insulators, we theoretically achieve rectification ratios over 140, a 10-fold improvement over the state of the art, with nanofilms of vanadium dioxide and cubic boron nitride in the parallel-plane geometry at experimentally feasible gap sizes (\ensuremath{\sim}100 nm). Our rational design offers relative ease of fabrication, flexible choice of materials, and robustness against deviations from optimal film thicknesses. We expect this work to facilitate the application of thermal diodes in solid-state thermal circuits and energy-conversion devices.

We present results for the electronic and magnetic structure of Mn and Fe clusters on Nb(110) surface, focusing on building blocks of atomic chains as possible realizations of topological superconductivity. The magnetic ground states of the atomic dimers and most of the monatomic chains are determined by the nearest-neighbor isotropic interaction. The dependence on the crystallographic direction as well as on the atomic coordination number is analyzed via an orbital decomposition of this isotropic interaction based on the spin-cluster expansion and the difference in the local density of states between ferromagnetic and antiferromagnetic configurations. A spin-spiral ground state is obtained for Fe chains along the [$1\overline{1}0$] direction as a consequence of the frustration of the isotropic interactions. Here, a flat spin-spiral dispersion relation is identified, which can stabilize spin spirals with various wave vectors together with the magnetic anisotropy. This may lead to the observation of spin spirals of different wave vectors and chiralities in longer chains instead of a unique ground state., Comment: 13 pages, 6 figures, 5 tables

For the pristine phosphorene nanoribbons (PNRs) with edge states, there exist two categories of edge bands near the Fermi energy (${E}_{F}$), i.e., the shuttle-shaped twofold-degenerate and the near-flat simple degenerate edge bands. However, the usual experimental measurement may not distinguish the difference between the two categories of edge bands. Here we study the varying rule for the edge bands of PNRs under an external electrostatic field. By using the KWANT code based on the tight-binding approach, we find that the twofold-degenerate edge bands can be divided into two separated shuttles until the degeneracy is completely removed and a gap near ${E}_{F}$ is opened under a sufficiently strong in-plane electric field. Importantly, each shuttle from the ribbon upper or lower edge outmost atoms is identified according to the local density of states. However, under a small off-plane field the shuttle-shaped bands are easily induced into two near-flat bands contributed from the edge atoms of the top and bottom sublayers, respectively. The evidence provides the edge and sublayer degrees of freedom (DOF) for the PNRs with shuttle-shaped edge bands, which is obviously different from another category of PNRs intrinsically with near-flat edge bands. This is because the former category of ribbons solely have four zigzaglike atomic configurations at the edges in each unit cell, which also results in that the property is robust against the point defect in the ribbon center area. As an application, furthermore, based on this issue we propose a homogenous junction of a shuttle-edge-band PNR attached by two electric gates. Interestingly, the transport property of the junction with field manipulation well reflects the characteristics of the two DOFs. These findings may provide a further understanding on PNRs and initiate new developments in PNR-based electronics.

We propose theoretically a tunable circular Bragg microcavity to enhance the intensity of the emission band of interest in rare-earth-doped materials and to suppress the unwanted emission bands which produce noise and diminish the efficiency of the emission band of interest. The surrounding of the microcavity comprises of alternating layers of high-index and low-index materials. The luminescent ions such as neodymium Nd3+ having different emission bands in different host materials are placed in the microcavity, and single emission band with stronger intensity can be observed, and other emission bands are suppressed. The wavelength of the single emission peak can be changed from one wavelength to other wavelengths by varying the refractive index, radius of the microcavity and thus modifying the local density of state of the microcavity. The fluorescence branching ratio of emission band of interest can be enhanced from 10% to 100% due to suppression of the unwanted emission bands.

In this work we study the frontal collision of protons with the carbon atoms of a graphene surface with a low coverage of adsorbed potassium. It is aimed at the analysis of the effect of the adsorbates in both charge exchange and electron emission processes, when the binary collision occurs between the proton and a carbon atom of the surface. The frontal collision with the K adsorbate, already analyzed and discussed in a previous work, is compared with the frontal collision with different carbon neighbors. In the present work we studied the signals, due to the localized structures in the density matrix of the composed graphene plus potassium surface, that can be distinguished when the collision occurs either with the adsorbate, a nearby carbon atom, or a carbon atom that does not feel the presence of the adsorbate. The interacting system is described by the Anderson Hamiltonian which takes into account the electronic repulsion on the projectile site; the charge fractions, the energy distribution of electrons in the solid, and the electron emission after the collision are calculated by using the nonequilibrium Green-Keldysh functions formalism solved by the equation of motion method. In the binary collision with a carbon atom, the extended features of the band structure of graphene smooth the dependence of the projectile charge fractions on the incoming energy and notably decrease the negative ions formation. The localized structures of the density of matrix caused by the presence of the adsorbate are perceptible for scattered carbon atoms close to K. The intense emission of low energy electrons obtained in the case of the scattering by potassium is fundamentally associated with the very localized K-4s empty band. This characteristic, although less marked, remain in the scattering by nearby carbon atoms, due to both the interaction with K along the projectile trajectory and the perturbed local density of states on the carbon atoms due to the adsorbate presence. In addition, the extended nature of the electronic structure of graphene allows for the emission of more energetic electrons. Fil: Iglesias García, Adalberto de Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina Fil: Romero, M. A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina Fil: García, Evelina Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina Fil: Goldberg, Edith Catalina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina

We study, both experimentally and theoretically, the modification of ${\mathrm{Er}}^{3+}$ photoluminescence properties in $\mathrm{Si}$ dielectric nanoslots. The ultrathin nanoslot (down to 5-nm thickness), filled with $\mathrm{Er}$ in ${\mathrm{Si}\mathrm{O}}_{2}$, boosts the electric and magnetic local density of states via coherent near-field interaction. We report an experimental 20-fold enhancement of the radiative decay rate with negligible losses. Moreover, via modifying the geometry of the all-dielectric nanoslot, the outcoupling of the emitted radiation to the far field can be strongly improved, without affecting the strong decay-rate enhancement given by the nanoslot structure. Indeed, for a periodic square array of slotted nanopillars an almost one-order-of-magnitude-higher ${\mathrm{Er}}^{3+}$ PL intensity is measured with respect to the unpatterned structures. This has a direct impact on the design of more efficient CMOS-compatible light sources operating at telecom wavelengths.

An ionic liquid-based thin (~ 1 µm) colorimetric membrane (CM) is a key nano-tool for optical ion sensing, and a two-dimensional photonic crystal slab (PCS) is an important nano-platform for ultimate light control. For highly sensitive optical ion sensing, this report proposes a hybrid of these two optical nano-elements, namely, a CM/PCS hybrid. This structure was successfully fabricated by a simple and rapid process using nanoimprinting and spin-coating, which enabled control of the CM thickness. Optical characterization of the hybrid structure was conducted by optical measurement and simulation of the reflection spectrum, indicating that the light confined in the holes of the PCS was drastically absorbed by the CM when the spectrum overlapped with the absorption spectrum of the CM. This optical property obtained by the hybridization of CM and PCS enabled drastic improvement in the absorption sensitivity in Ca ion sensing, by ca. 78 times compared to that without PCS. Experimental and simulated investigation of the relation between the CM thickness and absorption sensitivity enhancement suggested that the controlled light in the PCS enhanced the absorption cross-section of the dye molecules within the CM based on the enhanced local density of states. This highly sensitive optical ion sensor is expected to be applied for micro-scale bio-analysis like cell-dynamics based on reflectometric Ca ion detection.

We theoretically investigate the application of topological plasmon polaritons (TPPs) to temperature sensing for the first time. Based on an analogy of the topological edge states in the Su-Schrieffer-Heeger model, TPPs are realized in a one-dimensional intrinsic indium antimonide (InSb) microsphere chain. The existence of TPPs is demonstrated by analyzing the topology of the photonic band structures and the eigenmode distribution. By exploiting the temperature dependence of the permittivity of InSb in the terahertz range, the resonance frequency of the TPPs can be largely tuned by the temperature. Moreover, it is shown that the temperature sensitivity of the TPP resonance frequency can be as high as $0.0264~\mathrm{THz/K}$ at room temperature, leading to a figure of merit over 150. By calculating the LDOS near the chain, we further demonstrate that the temperature sensitivity of TPPs is experimentally detectable via near-field probing techniques. This sensitivity is robust since TPPs are highly protected modes immune to disorder and can achieve a strong confinement of radiation. We envisage these TPPs can be utilized as promising candidates for robust and enhanced temperature sensing., 6 pages, 4 figures. comments are welcome

Recent experimental results have depicted a strong modification of the magnetic map when oxygen is added to Fe/Cr multilayers. Within ab initio DFT + U code we show that the Fe/O/Cr/Fe(001) semi-infinite system is unstable whereas oxygen tends to move on top of the Fe atomic layer. Focuss is therefore made on the O/Fe/Cr/Fe(001) semi-infinite slab which displays an interlayer exchange coupling different from the classical case when O is absent. The effect of the oxygen adsorbed layer is to alter strongly the local density of states on the Fe atoms: this can explain the modification of the interlayer exchange coupling. Both DFT-only and DFT + U approaches are investigated in order to point out the major effect of U on the magnetic polarization.

Electronic band structure modification of carbon nanotubes (CNTs) through Suzuki coupling has been predicted recently. Here, scanning tunneling microscopy/spectroscopy studies of a molecular junction developed through C–C coupled CNTs are conducted to probe the local density of states variation along the junction, and the distorted band structure of CNT at the junction is unraveled, in agreement with the predictions. The band structure modification aided by charge transfer, among CNTs and C6H4 in the junction, helps to achieve a more efficient *COOH adsorption in coupled CNTs (CCNTs) than in pristine CNTs, proven via density functional theory-based calculations. This indicates the possibilities of CCNT-based electrochemical CO2 reduction. Formate production at low potential (−0.9 V vs reversible hydrogen electrode) in neutral pH (6.8) is demonstrated with CCNT, while no formic acid production is observed in uncoupled CNTs. This study opens a fundamental insight into the development of novel catalysts base...

Exploring the structural transformation of nonhexagonal rings is of fundamental importance for understanding the thermal stability of nonhexagonal rings and revealing the structure–property relationships. Here, we report on the thermally induced transformation from the fused tetragon-hexagon (4–6) carbon rings to a pair of pentagon (5–5) rings in the graphene-like nanoribbons periodically embedded with tetragon and octagon (4–8–4) carbon rings. A distinct contrast among tetragon, pentagon, hexagon, and octagon carbon rings is provided by noncontact atomic force microscopy with atomic resolution. The thermally activated bond rotation with the dissociation of the shared carbon dimer between the 4–6 carbon rings is the key step for the 4–6 to 5–5 transformation. The energy barrier of the bond rotation, which results in the formation of an irregular octagon ring in the transition state, is calculated to be 1.13 eV. The 5–5 defects markedly change the electronic local density of states of the graphene-like nan...

By using density functional theory (DFT) and nonequilibrium Green's function (NEGF), field effect transistor (FET) based on zigzag shaped phosphorene nanoribbons (ZPNR) are investigated. The FETs are constructed with bare-edged ZPNRs as electrodes and H, Cl or OH adsorbed ZPNRs as channel. It is found FETs with the three kinds of channel show similar transport properties. The FET is p-type with a maximum current on/off ratio of 104 and a minimum off-current of 1 nA. The working mode of FETs is dependent on the parity of channel length. It can be either enhancement mode or depletion mode and the off-state current shows an even-odd oscillation. The current oscillations are interpreted with density of states (DOS) analysis and methods of evolution operator and tight-binding Hamiltonian. Operating mechanism of the designed FETs is also presented with projected local density of states and band diagrams.

We studied the electronic transport properties of a 4 QL thin Bi 2 Se 3 film in the hybridized phase on Si(111) by scanning tunneling potentiometry. When a transverse voltage is applied, the film exhibits a homogeneous electric field on the nm scale. In addition, thermovoltage signals with lateral nm variations are found which result from sample heating by the transverse current. The thermovoltage signals are directly correlated to morphological structures on the surface, i.e. step edges, and indicate a lateral variation of the local density of states at the Bi 2 Se 3 surface. No discernible voltage drops appear at the surface so that the whole film serves as a current carrying medium and scattering at surface defects is less important.

Spectroscopic and nanoscale imaging investigations concerning the spatial extent of molecular orbitals at organic/substrate interfaces have been of intense interest to understand charge dynamics. Here, the spatial extent of unoccupied molecular orbitals of ultrathin rubrene [5,6,11,12-tetraphenyltetracene] films has been investigated with scanning tunneling microscopy and spectroscopy. Based on constant-current distance (z)-voltage (V) measurements, the unoccupied energy levels are elucidated and found to be consistent with previously reported macroscopic two-photon photoemission (2PPE) spectroscopy. In the diffuse unoccupied molecular orbitals reported with 2PPE (J. Phys. Chem. C, 2013, 117, 20098), nanoscale dz/dV spatial maps reveal that the local density of states of the orbitals extends over the rubrene molecules. Delocalization is also observed for the image potential states, which are inherently free-electron-like. This is in contrast to the localized nature of other unoccupied molecular orbitals. A nanoscale understanding of diffuse and delocalized molecular orbitals provides a fundamental insight into low-lying Rydberg states in polycyclic aromatic hydrocarbons.

In this study, the effects of Ge modification of Si anodes in Si–Ge air batteries were investigated by building various atomic models of Si/Ge/GeO2 interfaces and performing density functional theory calculations. The results showed that the surface passivation could be restrained effectively by Ge modification because the adsorption energies of the GeO2 units on the Si–Ge anode increased when more Si atoms were substituted by Ge atoms. The electrostatic difference potentials, electron densities, and projected local density of states were also calculated for various Si/Ge/GeO2 interfaces to determine the differences in the properties of the Si-air battery and Si–Ge air battery. In addition, the I–V curves showed that the Si/Ge/SiO2/Si devices had higher currents than the Si/SiO2/Si device and the currents could be modulated by modification with Ge atoms. These findings provide insights into the mechanism responsible for the enhanced properties obtained by modification with Ge and they may facilitate the design of Si–Ge composite anodes for use in air batteries.

For the first time, a strong anisotropy of electrical conductance is established in graphene films with regular holes, graphene films with vertically aligned armchair carbon nanotubes (CNTs) seamlessly bonded to graphene, and monolayer pillared graphene films. Electrical conductance along the armchair direction is 3–7 times larger than that along the zigzag direction. Also, a prominent oscillation in electrical conductance along the armchair direction is first discovered. This effect is clearly manifested when the CNT length is increased by atomic layers. In this case, the electrical conductance oscillation can reach 80–90% and the oscillation frequency is equal to three.

The quantum confinement effect on the spectrum of near-field thermal radiation by periodic and random arrays of quantum dots (QDs) is investigated. The local density of states (LDOS) thermally emitted by QD arrays made of three lead chalcogenides, namely, lead sulfide, lead selenide, and lead telluride, is computed at a near-field distance from the arrays. The dielectric function of the QDs is extracted from their absorption spectra by utilizing an optimization technique. The thermal discrete dipole approximation is used for computing the LDOS. It is shown that the peak wavenumber of near-field LDOS emitted by periodic arrays of lead chalcogenide QDs can be significantly modulated (up to 4490 cm−1) by varying the size of the dots. The LDOS is proportional to the imaginary part of the QDs' polarizability, which peaks at the bandgap energy of the QDs. The bandgap energy of the QDs (and thus the LDOS peak) is significantly affected by the quantum confinement effect, which is size dependent. While the magnitude of thermal radiation by random arrays of QDs can be different from the periodic arrays with the same filling factor by up to ±26%, the LDOS spectrum and peak location are the same for both periodic and random arrays. The peak wavenumber of near-field radiative heat transfer between the QD arrays is also strongly affected by quantum confinement in the QDs, and thus, it can be tuned by changing the size of the QDs.

The electronic properties of metal-molecule interfaces can in principle be controlled by molecular design and self-assembly, yielding great potential for future nano- and optoelectronic technologies. However, the coupling between molecular orbitals and the electronic states of the surface can significantly influence molecular states. In particular, molecules designed to create metal-organic self-assembled networks have functional groups that by necessity are designed to interact strongly with metals. Here, we investigate the adsorption interactions of a terpyridine (tpy)-based molecule on a noble metal, Ag(111), by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) together with density functional theory (DFT) calculations. By comparing the local density of states (DOS) information gained from STS for the molecule on the bare Ag(111) surface with that of the molecule decoupled from the underlying metal by a NaCl bilayer, we find that tpy-localized orbitals hybridize strongly with the metal substrate. Meanwhile, those related to the phenyl rings that link the two terminal tpy groups are less influenced by the interaction with the surface. The selective hybridization of the tpy groups provides an example of strong, orbital-specific electronic coupling between a functional group and a noble-metal surface, which may alter the intended balance of interactions and resulting electronic behavior of the molecule-metal interface.

We investigated the adhesion behavior and electronic properties of an epoxy adhesive on an α-Fe 2 O 3 (0001) surface using density functional theory (DFT). We found the significant attractive interactions including cation–π interactions between the aromatic rings and the Fe 2 O 3 surface, and the electrostatic interactions between the O atom of the hydroxyl group and the Fe atoms of the Fe 2 O 3 surface. Upon adsorption of the epoxy adhesive, local density of states (LDOS) analysis reveals an overall broadening of peaks as well as band gap narrowing, indicating that changes to the electronic properties of the surface occur along with charge transfer.

Modulation of the local density of states of single-wall carbon nanotubes (SWCNTs) is induced by the encapsulation of europium nanowires (EuNWs). The observation of these modulated density of states using scanning tunneling microscopy/spectroscopy combined with density functional theory calculations is reported. The electronic modulation of SWCNTs by encapsulation of EuNWs is revealed as a Fermi level shift, band gap reduction, and the emergence of localized states in the gap. The present results show that the electronic interaction between EuNWs and SWCNTs is much stronger than that previously reported for nanomaterials encapsulated in SWCNTs.

Scanning tunneling spectroscopy measures how a single electron with definite energy propagates between a sample surface and the tip of a scanning tunneling microscope. In the simplest description, the differential conductance measured is interpreted as the local density of states of the sample at the tip position. This picture, however, is insufficient in some cases, since especially smaller molecules weakly coupled with the substrate tend to have strong Coulomb interactions when an electron is inserted or removed at the molecule. We present theoretical approaches to go from the non-interacting and single-particle picture to the correlated many-body regime. The methodology is used to understand recent experiments on finite armchair graphene nanoribbons and phthalocyanines. We also theoretically discuss the strongly-correlated model system of fractional quantum Hall droplets., Submitted to Journal of Electron Spectroscopy and Related Phenomena

Surface phonon polariton supported by silicon carbide (SiC) can be strongly coupled with graphene plasmon in the graphene-covered SiC bulk. The spectrum of the electromagnetic local density of states exhibits two peaks whose positions can be tuned by the chemical potential of graphene. In this work, we study the electromagnetic local density of states in the proximity of a graphene-covered SiC with periodic hole arrays. The well-known peak from the coupling of surface polariton supported by SiC and graphene plasmon splits into two. With increased volume ratio of holes, one of the split peak shifts towards high frequencies, whereas the other moves towards low frequencies. The dependence of split-peak positions on the chemical potential and permittivity of filling materials in the holes are also investigated. This study offers another method of modulating the electromagnetic local density of states.

Using density functional theory (DFT), combined with non-equilibrium Green’s function (NEGF) method, the effect of potential change, charge distribution, voltage drop, band lineup, and evolution of the transmission spectrum under small applied bias for a memantine-functionalized gold nanogap device for DNA detection have been studied in this report. We have investigated the potential perturbation and charge distribution introduced by the electrodes and the nucleobases separately, which helps to understand the development of the potential profile throughout the molecular break junction and the effect on the transmission spectrum. The presence of electrodes is found to modify the energy levels and band lineup of the device. We have also investigated the local density of states to understand the contact- and nucleobase-modified charge distributions in the molecular states. The electronic wave functions for the HOMO transmission peak at various applied voltages are also examined to understand the physics behi...

The influence of chemical side groups is significant in physical or chemical understanding the transport through the single molecular junction. Motivated by the recent successful fabrication and measurement of a single organic molecule sandwiched between graphene electrodes (Prins et al., 2011), here we study the spin-dependent transport properties through a junction of a fused oligothiophenes molecule embedded between two zigzag-edged graphene nanoribbon (ZGNR) electrodes. The molecule with and without an attached amino NH 2 side group is considered, respectively, and external magnetic fields or FM stripes are applied onto the ZGNRs to initially orient the magnetic alignment of the electrodes for the spin-dependent consideration. By the ab initio calculations based on the density functional theory combined with nonequilibrium Green’s function formalism, we have demonstrated the remarkable difference in the spin-charge transport property between the junctions of the molecule with and without NH 2 side group. In particular, the junction with side group shows more obvious NDR. In addition, it exhibits an interesting dual spin-filtering effect when the magnetic alignment in electrodes is initially antiparallel-oriented. The mechanisms of the results are revealed and discussed in terms of the spin-resolved transmission spectrum associated with the frontier molecular orbitals evolution, the molecular projected self-consistent Hamiltonian eigenvalues, and the local density of states.

The electronic transport properties of the carbon atomic chain in combination with a stand-up attached polyacetylene (C\(_n\)H\(_n\) + 1) molecule sandwiched between two zigzag graphene nanoribbon electrodes, were investigated based on the density-function theory and the nonequilibrium Green's functions approach. Our calculation shows that the transport behavior is sensitive to the number of carbon atoms on the C\(_n\)H\(_n\) + 1 chains. Specifically, we demonstrate that the transport properties of even-n C\(_n\)H\(_n\) + 1 devices behave much stronger than the odd ones; in addition, the odd-n C\(_n\)H\(_n\) + 1 devices provide well-matched resonance transport channels between the transverse carbon chain and stand-up attached C\(_n\)H\(_n\) + 1 chains, which induces the isolated transmission peak at the Fermi level. So an abnormal even–odd oscillation in conductance in terms of the number of carbon atoms on C\(_n\)H\(_n\) + 1 chains can be found. On the other hand, the striking negative differential resistance behaviors appear in the proposed devices. The mechanisms are analyzed and revealed by the local density of states around the Fermi level at zero bias, with the evolution of the molecular projected self-consistent Hamiltonian associated with the transmission spectrum under different applied bias.

Switching the magnetic properties of organic semiconductors on a metal surface has thus far largely been limited to molecule-by-molecule tip-induced transformations in scanned probe experiments. Here we demonstrate with molecular resolution that collective control of activated Kondo screening can be achieved in thin-films of the organic semiconductor titanyl phthalocyanine on Cu(110) to obtain tunable concentrations of Kondo impurities. Using low-temperature scanning tunneling microscopy and spectroscopy, we show that a thermally activated molecular distortion dramatically shifts surface-molecule coupling and enables ensemble-level control of Kondo screening in the interfacial spin system. This is accompanied by the formation of a temperature-dependent Abrikosov-Suhl-Kondo resonance in the local density of states of the activated molecules. This enables coverage-dependent control over activation to the Kondo screening state. Our study thus advances the versatility of molecular switching for Kondo physics and opens new avenues for scalable bottom-up tailoring of the electronic structure and magnetic texture of organic semiconductor interfaces at the nanoscale.

We provide here a full analysis of the ground state properties of Tricalcium silicate Ca3SiO5 (C3S) by means of density functional theory. Elastic behaviour of C3S was characterized by considering the stable phase and anisotropy of this material. Moreover, the electronic structure is determined in order to get an insight into the reaction mechanism of C3S. Local density of states (LDOS) of valence band maximum (VBM) and conduction band minimum (CBM) are analysed to characterize reactive sites of C3S. Two oxygen atom-types were distinguished from the charge density of the system. LDOS of VBM is highly localized explaining the observed high reactivity of C3S under electrophilic attacks (e.g. H+). In addition, reactive sites under electrophilic attacks are noticed to be only around some specific oxygen atoms. In contrast, the analysis of LDOS for CBM suggests that some calcium atoms are responsible for undergoing reaction with anions such as hydroxide ion.

The electronic and transport properties of the monolayer black phosphorus and germanene nanoribbons are studied in the framework of the tight-binding model (TBM) based upon Landauer-Buttiker formalism using Green’s function method (GFM). The local density of states (LDOS) and electronic conductance of the phosphorene and germanene nanoribbons along zigzag and armchair directions are examined when the various types of defects are introduced into the system. It is found that the transport properties of zigzag phosphorene and germanene nanoribbons are strongly dependent on the number and location of the vacancies. Furthermore, it is shown that the one-/three-atom vacancy induces quasi-states in the conductance around the Fermi energy because of breaking the sublattice symmetry in the zigzag germanene nanoribbons (ZGeNRs). So the metal-semiconductor transition occurs when one-/three-atom vacancy is located at the edges of ZGeNRs; however, this transition is not observed in the zigzag phosphorene nanoribbons (ZPNRs). Besides, the results of the calculations indicate more sensitivity of ZPNRs on conductivity to the edge vacancy disorders than armchair phosphorene nanoribbons (APNRs). In addition, the conductance of ZPNRs decreases with the increment of the ribbon width in the presence of edge vacancy. Importantly, the disappearance of conductance around Fermi energy in ZPNR due to Anderson localization disorder highlights an important conclusion for the possibility of quenching of the conductance near the Fermi energy, making this class of materials appealing for applications in digital transistor devices.

High-temperature thermal photonics presents unique challenges for engineers as the database of materials that can withstand extreme environments are limited. In particular, ceramics with high temperature stability that can support coupled light-matter excitations, that is, polaritons, open new avenues for engineering radiative heat transfer. Hexagonal boron nitride (hBN) is an emerging ceramic 2D material that possesses low-loss polaritons in two spectrally distinct mid-infrared frequency bands. The hyperbolic nature of these frequency bands leads to a large local density of states (LDOS). In 2D form, these polaritonic states are dark modes, bound to the material. In cylindrical form, boron nitride nanotubes (BNNTs) create subwavelength particles capable of coupling these dark modes to radiative ones. In this study, we leverage the high-frequency optical phonons present in BNNTs to create strong mid-IR thermal antenna emitters at high temperatures (938 K). Through direct measurement of thermal emission of a disordered system of BNNTs, we confirm their radiative polaritonic modes and show that the antenna behavior can be observed even in a disordered system. These are among the highest-frequency optical phonon polaritons that exist and could be used as high-temperature mid-IR thermal nanoantenna sources.

In this paper we present state of the art coupled-mode space based Non-Equilibrium Green Function approach for modeling quantum transport accurately in the vertically stacked Silicon nanowire (SiNW) FETs. Random discrete dopants (RDD) and metal grain granularity (MGG) induced variability in stacked SiNW FETs are also investigated. Furthermore, charge spectrum, current spectrum w.r.t. sub bands and the space-resolved Local Density of States (LDOS) corresponding to the location of band edge are analyzed in detail. The newly developed flexible and computationally efficient models implemented in quantum transport simulation tool NESS provides valuable insights on the effect of RDD and MGG variability on Sub-Threshold Swing (SS), Threshold Voltage $( \mathrm {V}_{TH})$ shift, On/Off Current $( \mathrm {I}_{ON}/ \mathrm {I}_{OFF})$ ratio and quantum confined charge transport mechanism.

Equiatomic quaternary Heusler compounds (EQHCs) generally have the advantages of high Curie temperature, large spin polarization and long spin diffusion length, and they are regarded as one of the most promising candidates for spintronics devices. Herein, we report a theoretical investigation on an EQHC CoRhMnGe based magnetic tunnel junction (MTJ) with (i) MnGe-terminated interface and (ii) modified pure Mn terminated interface, i.e., MnMn-terminated interface. By employing first principle calculations combined with non-equilibrium Green's function, the local density of states (LDOS), transmission coefficient, spin-polarized current, tunnel magnetoresistance (TMR) ratio and spin injection efficiency (SIE) as a function of bias voltage are studied. It reveals that when the MTJ under equilibrium state, TMR ratio of MnGe-terminated structure is as high as 3,438%. When the MTJ is modified to MnMn-terminated interface, TMR ratio at equilibrium is enhanced to 2 × 105%, and spin filtering effects are also strengthened. When bias voltage is applied to the MTJ, the TMR ratio of the MnGe-terminated structure suffers a dramatic loss. While the modified MnMn-terminated structure could preserve a large TMR value of 1 × 105%, even bias voltage rises up to 0.1 V, showing a robust bias endurance. These excellent spin transport properties make the CoRhMnGe a promising candidate material for spintronics devices.

Graphene grown directly on germanium is a possible route for the integration of graphene into nanoelectronic devices as well as it is of great interest for materials science. The morphology of the interface between graphene and germanium influences the electronic properties and has not already been completely elucidated at atomic scale. In this work, we investigated the morphology of the single-layer graphene grown on Ge substrates with different crystallographic orientations. We determined the presence of sinusoidal ripples with a single propagation direction, zig-zag, and could arise due to compressive biaxial strain at the interface generated as a result of the opposite polarity of the thermal expansion coefficient of graphene and germanium. Local density of states measurements on the ripples showed a linear dispersion relation with the Dirac point slightly shifted with respect to the Fermi energy indicating that these out-of-plane deformations were n-doped, while the graphene regions between the highs were undoped.

Compared with pristine ZrCo(110), the adsorption, dissociation, and successive diffusion of hydrogen on the Ti-decorated ZrCo(110) have been investigated based on first-principles calculation. For the purpose of having fast absorption kinetics, both activation processes need to overcome small energy barriers. The adsorption energies of molecular as well as atomic hydrogen on the Ti-decorated ZrCo(110) surface were calculated using first-principles calculations with the periodic density functional theory (DFT). The H2 molecule on ZrCo(110) and Ti-doped ZrCo(110) surfaces could be spontaneously partially dissociated due to the interaction with the substrate surfaces, producing H atoms strongly chemisorbed to the hollow sites. The H2 dissociation energy barrier and the H diffusion barrier were also determined. Our results show that the activation energy for H2 dissociation on the decorated surface (0.052 eV) is much smaller than that of the pure surface (0.524 eV), elucidating that the activation condition of H2 on the pure ZrCo(110) is more severe than that on the Ti-doped surface. Particularly, Ti-decoration facilitates the H2 dissociation. Moreover, the re-desorption performance of the two dissociated H atoms is improved by lowering the energetic barrier from 1.798 eV (on the pure surface) to 1.315 eV (on the decorated surface). The calculations also reveal that decorating the surface with Ti eliminates the barrier for the into-bulk penetration of a hydrogen atom. Based on the local density of states, the Bader charge and differential charge density, as well as the influence of the Ti atom on topological properties were analyzed. Theoretical results presented in this study are generally in well accordance with the available theoretical and experimental data.

We report investigation of the geometry and electronic structure of iridium atoms adsorbed onto graphene through a combined experimental and theoretical study. Ir atoms were deposited onto a flake of graphene on a Pt(111) surface and found to form clusters even at low temperatures. The areal density of the observed clusters on the graphene flake suggests the clusters are most likely pairs of Ir atoms. Theoretical ab initio density functional (DFT) calculations indicate that these Ir dimers are oriented horizontally, near neighboring >bridge> sites of the graphene lattice, as this configuration has the strongest adsorption energy of all high-symmetry configurations for the Ir dimer. A large peak in the local density of states (LDOS) at the Dirac point energy was measured via scanning tunneling spectroscopy, and this result is reproduced by a DFT calculation of the LDOS. The peak at the Dirac point energy is found to be from the Ir s and p states. The LDOS in the monomer case was also calculated, and is found to significantly differ from the experimentally determined data, further supporting the hypothesis of low-temperature clustering., This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract No. DE-AC02-05-CH11231, within the sp2-Bonded Materials Program (KC2207), (DFT simulated electronic structure and STM spectroscopy). Support was also provided by National Science Foundation Grants No. DMR-1508412 (diffusivity analysis) and No. DMR-1807233 (sample preparation). Computational resources have been provided by the DOE at Lawrence Berkeley National Laboratory’s NERSC facility.

Significant interest in two-dimensional transition metal dichalcogenides has led to numerous experimental studies of their synthesis using scalable vapor phase methods, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). ALD typically allows lower deposition temperatures, and nucleation of chemical precursors requires reactions with surface functional groups. A common first-principles method used to study ALD modeling is the calculation of activation energy for a proposed reaction pathway. In this work we calculated the partial charge densities, local density of states (LDoS), Bader charge analysis, adsorption energies, and charge density difference using density functional theory (DFT) to investigate the nucleation of MoF6 on three oxide surfaces, including Al2O3, HfO2, and MgO. Our findings indicate that hydroxyl groups (OH) help lower the reaction barrier during the first half-cycle of MoF6 and promote the chemisorption of a precursor on the oxide substrates. This discovery is supported by the formation of highly ionic MFx (M = metal, x = 1, 2, 3) bonds at the oxide surfaces. By comparing surfaces with and without hydroxyl groups, we highlight the importance of surface chemistry.

Tuning thermal transport in semiconductor nanostructures is of great significance for thermal management in information and power electronics. With excellent transport properties, such as ballistic transport, immunity to point defects and disorders, and forbidden backscattering, topological phonon surface states show remarkable potential in addressing this issue. Herein, topological phonon analyses are performed on hexagonal wurtzite gallium nitride (GaN) to check the topological characteristics of phonons. And other nitrides of the same family, i.e., AlN and AlGaN crystals, are also calculated from a topological phonon phase transition perspective. With the aid of first-principle calculations and topological phonon theory, Weyl phonon states, which host surfaces states without backscattering, are investigated for all these materials. The results show that there is no nontrivial topological phonon state in GaN. However, by introducing Al atoms, i.e., in wurtzite type AlN and AlGaN, more than one Weyl phonon point is found, confirmed by obvious topological characteristics, including non-zero integer topological charges, source/sink in Berry curvature distributions, surface local density of states, and surface arcs. As AlN and AlGaN are typical materials in AlGaN/GaN heterostructure based electronics, the existence of topological phonon states in them will benefit thermal management by facilitating the design of one-way interfacial phonon transport without backscattering.

The adsorption and hydrogenation behaviors of hydrogen cyanide to methane and ammonia formation by W(111) catalyst were systematically investigated using the density functional theory method. Based on our calculated consequences, it is found that the WHCN(T,T-μ2-C,N) is calculated to be the most stable conformer, possessing an adsorption energy of −49.8 kcal/mol, among all calculated structures of HCN/W(111) system. To comprehend the electronic property of its interaction between the adsorbate and substrate, we calculated the electron localization functions, local density of states, and Bader charges; our results were consistent and explicable. Reaction paths in all possible mechanisms were explored in detail, involving the hydrogenation on different orientations of each adsorbate and the scission of the carbon–nitrogen bond. Before forming an imine intermediate (H2CNH(a)), two adsorbed hydrogen atoms will sequentially react with the nitrogen and then carbon atoms in the first and second hydrogenation ste...