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Transition-metal containing metal phthalocyanine (MPc) molecules are representative molecular magnets and their adsorption on two-dimensional metallic surfaces has been extensively studied. In/Si(111)-4×1 is a prototypical quasi-one-dimensional metallic surface made up of alternating In nanowires and Si Seiwatz chains. Here, we investigated the adsorption of MPc (M = Mn, Fe, Co) on In/Si(111)-4×1 using density functional theory calculations. We found that there are three locally stable adsorption sites of MPc, two on In nanowires and one on Seiwatz chains. Also, the stable orientation of MPc is different depending on adsorption sites. Among three MPc’s, MnPc are found to carry a finite magnetic moment of 1.6 ~ 2.1 μB in its three almost-degenerate adsorption structures. The interaction between MPc molecules and the In/Si(111)-4×1 surface turns out to occur via the charge transfer, and the charge transfer channel varies for different adsorption sites: Transition-metal 3dz2 and two N 2pz orbitals on In nanowires vs. four N 2pz orbitals on Seiwatz chains.

One-dimensional indium chains on Si(111) exhibit both temperature-and defect-induced perioddoubling (×2) structural transitions, and their natures have been focus of recent investigations. Using density functional perturbation theory calculations, we examined the vibrational properties of the room-temperature Si(111)In-4×1 structure. The phonon band structure revealed two unstable modes at the zone-boundary in the chain direction, which lead to a lattice instability towards a structure with parallel trimers. This lattice-instability-driven 4 × 2 structure is different from the low-temperature 4×2 (LT-4×2) structure (hexagon structure). The result suggests that the roomtemperature phase is neither a static 4×1 phase nor the dynamical fluctuation of the LT-4×2 phase. We demonstrate that the room-temperature phase is a dynamically fluctuating parallel-trimer 4×2 phase, and the fluctuations become suppressed near the defects to result in the defect-induced ×2 structure.

We report density functional theory calculations on the vacancy-induced magnetic properties of the wurzite GaN $$(10\bar 10)$$ surface. Among various intrinsic vacancies on the surface, we focus on the monatomic Ga and N vacancies. We have found two stable geometries of a surface Ga vacancy and one stable geometry of a surface N vacancy. Two stable surface Ga vacancy structures are shown to have magnetic moments of 3 μ B , which is the same as for the bulk Ga vacancy. Differently from the bulk N vacancy carrying null magnetic moment, the monatomic surface N vacancy has a finite magnetic moment of 1 μ B . These results support the experimental claim that the roomtemperature ferromagnetism observed in inorganic nanoparticles is due to surface vacancies and their complexes. We also present simulated scanning tunneling microscope images for comparison with those obtained in future experimental studies.

We report density-functional-theory calculations on vacancies on the ZnO\((10\bar 10)\) surface with the on-site Coulomb interaction correction. Zn and O vacancies and three different configurations of ZnO divacancies were examined considering all the possible charge states. Using the calculated vacancy formation energies, we constructed the phase diagram by spanning the allowed range of electronic and ionic chemical potential. Differently from the bulk where the divacancy is not stabilized at all, one configuration of surface divacancies can be stable in a certain region of the chemical potentials. Among all the stable vacancies, only the neutral and the singly negatively-charged monatomic Zn vacancies exhibit a finite magnetic moment of 1 μB, which implies that the surface Zn vacancies may be responsible for the experimentally-observed room-temperature ferromagnetism in ZnO nanocrystals.

We have investigated the vibrational properties of orthorhombic PtSi by performing first-principles calculations. The calculated phonon band structure shows unstable phonon modes around the Γ-point. The ionic displacement vectors associated with the unstable Γ-point phonon mode suggest a structural modulation to a lower-symmetry phase, which was confirmed by comparing the theoretical equations of states of the modulated (P212121) and the unmodulated (Pnma) PtSi. The symmetry-reduced modulated orthorhombic PtSi shows a phonon band gap. We attribute the origin of the phonon band gap to the separation of the low-frequency Pt phonon modes and the high-frequency Si phonon modes due to the large atomic mass difference between Pt and Si.

We investigated the structural and the binding properties of black phosphorus (black-P) by employing density functional theory (DFT) calculations in combination with various implementations of the van der Waals (vdW) interaction. Both the binding energy curve of the two isolated puckered layers and the equation of states of the bulk black-P suggest that the conventional generalized gradient approximation (GGA) functional is incapable of describing the interlayer vdW interaction. From the comparison of the seven different vdW implementations, the appropriate vdW schemes in describing layer-structured black-P are found to be either the Grimme’s dispersion correction (DFT-D2) or the optB86b vdW denisty-functional approach.

We report density functional theory calculations for the bulk ZnO divacancy in hexagonal ZnO and compare the results with the monatomic bulk vacancies. We find that the ZnO divacancy could be viewed as a tightly-bound state of a doubly-negative Zn vacancy and the doubly-positive O vacancy from the structural and the electronic points of view. The singly-positive ZnO divacancy is found to carry a magnetic moment of 1µB, but it can only be stabilized in very high p-type samples. Otherwise, the non-magnetic neutral divacancy is stable. These results suggest that the ZnO divacancies in the bulk region cannot play a significant role in stabilizing the recently-observed ferromagnetism in ZnO nanoparticles.

We have performed spin-polarized density functional theory calculations on κ-carbides, (Fe, Mn)3AlC, to investigate both the effect of different exchange-correlation functionals and the effect of Mn substitution. Differently from our previous calculations using the Perdew-Wang functional, Fe2MnAlC is found to be the most stable crystal among crystalline κ-carbides by using the Perdew, Burke, and Ernzerhof functional. Supercell calculations to simulate low Mn concentration show that substitutional Mn atoms hardly interact with each other and suggest that a random alloy model can be applied. The stabilization of Fe2MnAlC and its enhanced magnetization are attributed to the formation of a -Mn-C- linear chain structure.

We perform spin-polarized density functional theory calculations for a Zn vacancy on the ZnO(10 $\bar 1$ 0) surface. Two stable configurations of the surface Zn vacancy are found, and the activation energy barrier is estimated to be ∼0.01 eV. The lower energy configuration has a newly formed surface Zn-O bond to restore the bulk-like structure on the surface. Due to the newly formed bond, the vacancy state in the band gap is characterized by a complicated hybridization of neighboring surface and subsurface atoms and by a more extended electron density. Despite such a hybridization, the surface Zn vacancy is found to have a robust magnetic moment of 1 μ B , implying that surface Zn vacancies may be responsible for the ferromagnetism observed in ZnO thin films and nanoparticles. Simulated scanning tunneling microscope images show that the two structures of the surface Zn vacancy can be distinguished in the filled-state images.

The initial adsorption of oxygen molecules on Si(001) is investigated at room temperature. The scanning tunneling microscopy images reveal a unique bright O2-induced feature. The very initial sticking coefficient of O2 below 0.04 Langmuir is measured to be ∼0.16. Upon thermal annealing at 250–600 °C, the bright O2-induced feature is destroyed, and the Si(001) surface is covered with dark depressions that seem to be oxidized structures with -Si-O-Si- bonds. This suggests that the observed bright O2-induced feature is an intermediate precursor state that may be either a silanone species or a molecular adsorption structure.

We investigated the structural and the binding properties of tetrahedral P4 molecular pairs by employing density functional theory (DFT) calculations using both the local density approximation (LDA) and the generalized gradient approximation (GGA). To consider the van der Waals interaction, we employed the GGA with dispersion correction, specifically Grimme’s approach (DFT-D2). This DFT-D2 in conjunction with the GGA (GGA-D2) well fixes the failure of the GGA in reproducing a reasonable binding energy curve. The binding energy and the equilibrium intermolecular distance are found to be in close correlation with the number of adjacent atomic pairs between two molecules. Application of the LDA and the GGA-D2 to a molecular crystal β-P4 and comparison with experiments confirms that the GGA-D2 should be used for a reliable description of P4-based molecular systems.

The Cl-saturated Si(001) surface is investigated by employing density functional theory calculations. From the electronic density of states, the low- and the high-bias filled-state images and the empty-state images are found to originate from Cl(3p) states directed in-plane, in parallel with the Si dimer row, and perpendicular to the surface (z), respectively. The bright triplet, which is a characteristic scanning tunneling microscopy (STM) feature of an unchlorinated bare Si dimer, is attributed to an occupied dangling bond state of the bare Si dimer that is hybridized with the neighboring Cl(3pz) orbital. The previously observed split-dimer feature is confirmed to be the dimer-bond oxidized structure. Finally, we suggest that the initial back-bond oxidation does not occur on the chlorinated Si(001) surface because it is energetically not favored compared with dimer-bond oxidation and because its STM simulation does not match experimental images.