Search results for "DENSITY FUNCTIONAL THEORY"
showing 10 items of 981 documents
Optical and electronic properties of 2H−MoS2 under pressure: Revealing the spin-polarized nature of bulk electronic bands
2018
Monolayers of transition-metal dichalcogenide semiconductors present spin-valley locked electronic bands, a property with applications in valleytronics and spintronics that is usually believed to be absent in their centrosymmetric (as the bilayer or bulk) counterparts. Here we show that bulk $2\mathrm{H}\text{\ensuremath{-}}\mathrm{Mo}{\mathrm{S}}_{2}$ hides a spin-polarized nature of states determining its direct band gap, with the spin sequence of valence and conduction bands expected for its single layer. This relevant finding is attained by investigating the behavior of the binding energy of $A$ and $B$ excitons under high pressure, by means of absorption measurements and density-functi…
Role ofp-dands-dinteractions in the electronic structure and band gap of Zn1−xMxO (M=Cr, Mn, Fe, Co, Ni, and Cu): Photoelectron and optical spectrosc…
2012
We report an investigation on the effect of $p$-$d$ and $s$-$d$ interactions in the electronic structure, and especially in the band-gap value, of wurtzite wide-gap diluted magnetic semiconductors Zn${}_{1\ensuremath{-}x}$${M}_{x}$O ($M=\mathrm{Cr}$, Mn, Fe, Co, Ni, Cu). Thin films prepared by pulsed laser deposition are investigated by means of optical absorption at low-temperature and photoelectron spectroscopy. Pure wurzite phase is shown to be maintained for Co and Mn concentrations up to 25$%$ and for Cr up to 10$%$, while in the case of Fe, Ni, and Cu, other phases are present for concentrations higher than 5, 2, and 1$%$, respectively. The band gap of the Zn${}_{1\ensuremath{-}x}$${M…
Luminescent copper(i) complexes with bisphosphane and halogen-substituted 2,2′-bipyridine ligands
2018
Heteroleptic [Cu(P^P)(N^N)][PF6] complexes, where N^N is a halo-substituted 2,2'-bipyridine (bpy) and P^P is either bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) have been synthesized and investigated. To stabilize the tetrahedral geometry of the copper(I) complexes, the steric demands of the bpy ligands have been increased by introducing 6- or 6,6'-halo-substituents in 6,6'-dichloro-2,2'-bipyridine (6,6'-Cl2bpy), 6-bromo-2,2'- bipyridine (6-Brbpy) and 6,6'-dibromo-2,2'-bipyridine (6,6'-Br2bpy). The solid-state structures of [Cu(POP)(6,6'-Cl2bpy)][PF6], [Cu(xantphos)(6,6'-Cl2bpy)][PF6].CH2Cl2, [Cu(POP)(6-Brbpy)][PF6] and [Cu(xantp…
Ab Initio Simulation of Attosecond Transient Absorption Spectroscopy in Two-Dimensional Materials
2018
We extend the first-principles analysis of attosecond transient absorption spectroscopy to two-dimensional materials. As an example of two-dimensional materials, we apply the analysis to monolayer hexagonal boron nitride (h-BN) and compute its transient optical properties under intense few-cycle infrared laser pulses. Nonadiabatic features are observed in the computed transient absorption spectra. To elucidate the microscopic origin of these features, we analyze the electronic structure of h-BN with density functional theory and investigate the dynamics of specific energy bands with a simple two-band model. Finally, we find that laser-induced intraband transitions play a significant role in…
A theoretical analysis of the structure and properties of B26H30 isomers. Consequences to the laser and semiconductor doping capabilities of large bo…
2019
Decaborane(14), nido-B10H14, is the major commercially available molecular building block in boron cluster chemistry. The condensation of two such {nido-B10} blocks gives the known isomers of B18H22 – a molecule used in the fabrication of p-type semiconductors and capable of blue laser emission. Here, we computationally determine the structures and thermodynamic stabilities of 20 possible B26H30 regioisomers constructed from the fusion of three {nido-B10} blocks with the three subclusters conjoined by two-boron atom shared edges. In addition, density functional theory, time-dependent (TD)-DFT and multiconfigurational CASPT2 methods have been used to model and investigate the physical and ph…
Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites
2017
Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu2ZnGeS4-x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlyi…
Structural and Kinetic DFT Characterization of Materials to Rationalize Catalytic Performance
2009
This review shortly discusses recent results obtained by the application of density functional theory for the calculations of the adsorption and diffusion properties of small molecules and their reactivity on heterogenous catalytic systems, in the ambit of the Nanocat project. Particular focus has been devoted to palladium catalysts, either in atomic or small cluster form. Some protocols have been tested to obtain efficient ways able to treat the electronic and geometric influence of supports like zeolites and carbon nanotubes on the catalytic properties of palladium. The hydroisomerization of cis-but-2-ene is discussed as model reaction on supported and unsupported Pd clusters. Some prelim…
Isolation of a perfectly linear uranium(II) metallocene
2020
Reduction of the uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) with potassium graphite produces the "second-generation" uranocene [(eta(5)-(C5Pr5)-Pr-i)(2)U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f(3) 6d(1). Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbi…
H2 Transformations on Graphene Supported Palladium Cluster: DFT-MD Simulations and NEB Calculations
2020
Molecular dynamics simulations based on density functional theory were employed to investigate the fate of a hydrogen molecule shot with different kinetic energy toward a hydrogenated palladium cluster anchored on the vacant site of a defective graphene sheet. Hits resulting in H2 adsorption occur until the cluster is fully saturated. The influence of H content over Pd with respect to atomic hydrogen spillover onto graphene was investigated. Calculated energy barriers of ca. 1.6 eV for H-spillover suggest that the investigated Pd/graphene system is a good candidate for hydrogen storage.
Atlas for the properties of elemental two-dimensional metals
2018
Common two-dimensional (2D) materials have a layered three-dimensional (3D) structure with covalently bonded, atomically thin layers held together by weak van der Waals forces. However, in a recent transmission electron microscopy experiment, atomically thin 2D patches of iron were discovered inside a graphene nanopore. Motivated by this discovery, we perform a systematic density-functional study on atomically thin elemental 2D metal films, using 45 metals in three lattice structures. Cohesive energies, equilibrium distances, and bulk moduli in 2D are found to be linearly correlated to the corresponding 3D bulk properties, enabling the quick estimation of these values for a given 2D metal a…