An analytical model of the heat of chemisorption: A perturbation LCAO MO approach

An analytical LCAO MO perturbation model has been developed for treating the heat of chemisorption Q of an adsorbate A monolayer on a transition metal M film. The model combines parameters of the metal band (the Fermi level E_F, band width W = W^occ + W^vac, the d occupancy N_d, density of states n(?), etc.) with those of the local A-M interactions (the adorbital energy ?_A, off-diagonal matrix elements β_AM, etc.). The major cases of A's having lone pair, singly occupied, and vacant adorbitals have been considered, and the analytical expressions for Q as well as some numerical estimations are presented. The relative values of Q seem to be crucially dependent on the ratio β/(?_A ? E_F). The Q vs. N_d plots for the donor and radical A's are rather flat, typically Q decreasing monotonically as N_d increases, but for the acceptor A's the plots are very parameter dependent and show a variety of trends. The results obtained agree with straightforward computations and (scarce) experimental data.     

Electronically driven tetragonal distortion in TiH2

A study of the fluorite structure stoichiometric TiH₂ by means of the augmented plane wave method reveals that the density of states at the Fermi level is very high, due mainly to a degenerate flat band in the ΛL direction. This result, in agreement with the experimental data of Ducastelle, Caudron and Costa confirms their interpretation of the tetragonal distortion in terms of a Jahn-Teller type effect. The Fermi surface geometry is discussed in connection with the sign change of the observed Hall coefficient. A comparison with Switendick's previous work on hydrides is also given.     

Photoemission study of the adsorption of O2, CO and H2 on GaAs(110)

Ultraviolet photoemission spectroscopy with hv < 12 eV has been used to study O₂, CO, and H₂ adsorption on the cleaved GaAs(110) face. It was found that O₂ exposures above 10⁵ L(1LM = 10^?6 Torr sec) were required to produce changes in the energy distribution curves. At O₂ exposures of 10⁶ L on p-type and 10⁸ L on n-type an oxide peak is observed in the EDC's located 4 eV below the valence band maximum. On p-type GaAs, O₂ exposures cause the Fermi level at the surface to move up to a point 0.5 eV above the valence band maximum, while on n-type GaAs O₂ exposures do not remove the Fermi level pinning caused by empty surface states on the clean GaAs. CO was found to stick to GaAs, but to desorb over a period of hours, and not to change the surface Fermi level position. H₂ did not affect the EDC's, but atomic H lowered the electron affinity and raised the surface position of the Fermi level on p-type GaAs. A correlation is found in which gases which stick to the GaAs cause an upward movement of the Fermi level at the surface on p-type GaAs, while gases which stick only temporarily do not change the surface position of the Fermi level.     

Structure and properties of the intercalation compound Fe x TiTe2

The Fe _x TiTe₂ system, which belongs to the class of materials with the electronic spectrum containing below the Fermi level the band of localized states with a strong temperature dependence of the band width, has been investigated experimentally. Heating of the material leads to a broadening of the band of localized states. When the top of this band crosses with the Fermi level, the effect of retrograde solubility is observed in the system; i.e., the metal precipitates to the composition ensuring the absence of increase in the Fermi energy during heating. The influence of the band of localized states on the structure of the material and its magnetic and electrical properties has been analyzed.     

Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

Directionality of the metallic bonding in titanium carbide

The ionic-covalent bonding in TiC is studied within a CNDO parameterized cluster model. Distribution of charge density reveals a directionality of the Ti-Ti metal bond as observed in the Ti dimer. This directionality is particularly significant at the Fermi level because of hybridisation involving d_xy ,d_xy and d_yz types of states. However, in the presence of a carbon vacancy the directionality of the metal bond is not as clear with charge spilling over into the vacant lattice site. The directional nature of the Ti-Ti bond at the Fermi level remains fairly unchanged.     

Electronic structures,magnetic properties and band alignments of 3d transition metal atoms doped monolayer MoS2

Utilizing first-principles calculations, the electronic structures, magnetic properties and band alignments of monolayer MoS₂ doped by 3d transition metal atoms have been investigated. It is found that in V, Cr, Mn, Fe-doped monolayers, the nearest neighboring S atoms (S_NN) are antiferromagnetically polarized with the doped atoms. While in Co, Ni, Cu, Zn-doped systems, the S_NN are ferromagnetically coupled with the doped atoms. Moreover, the nearest neighboring Mo atoms also demonstrate spin polarization. Compared with pristine monolayer MoS₂, little change is found for the band edges' positions in the doped systems. The Fermi level is located in the spin-polarized impurity bands, implying a half-metallic state. These results provide fundamental insights for doped monolayer MoS₂ applying in spintronic, optoelectronic and electronic devices.     

Conduction electron distributions in europium and gadolinium by soft x-ray spectroscopy

A study of the 5d6s conduction band in Eu and Gd by soft X-ray spectroscopy is presented. Our observation that the density of occupied d states is lower for Eu than for Gd is supported by band structure calculations. For Gd, the convolution integrals between the 3p_3/2 inner level Lorentzian distribution and the A.P.W. densities of states are compared with our experimental M_m spectra. The position of the occupied 4f states with respect to the Fermi level is determined, compared with X-ray photoemission data and discussed for both metals.     

Hydrostatic pressure derivatives of the single crystal elastic moduli of Gd,Dy and Er

The hydrostatic pressure derivatives of the single crystal elastic moduli of Gd, Dy and Er have been measured at 298°K, to pressures near 5 Kbar. The very small pressure derivatives of the adiabatic bulk moduli indicate that a small ion core model should be appropriate for interpreting the data. The long-range electrostatic contributions to the shear moduli have a dominant influence on the pressure derivatives of the shear moduli of Er, whereas the Gd and Dy data evidently reflect band structure contributions. The values of the longitudinal stiffnesses correspond remarkably well with the Bohm-Staver model for velocity of waves in an ion plasma dispersed in a sea of electrons, where the ionic interaction is perely Coulombic. This model is extended to provide an interpretation of the volume derivatives of the longitudinal moduli in terms of the volume derivative of the density of electron states at the Fermi energy.The Grüneisen parameters calculated from averages of the acoustic model gammas are in relatively poor agreement with those determined from thermal expansion data. An explanation based on the changes in c/a ratio with volume change is tested quantitatively and found to be reasonably successful. The values of dK_T/dP, where K_T is the isothermal bulk modulus, are applied to the Murnaghan equation of state and give excelent agreement with Bridgman's direct compression data for Dy and Er to 40 Kbar. For Gd, Bridgman's data indicate either that (dK_T/dP)_p=0 should be considerably larger than deduced from the adiabatic dK_s/dP measurements or that a phase change occurs near 20 Kbar. The occurrence of a phase change in Er at ～90 Kbar is definitely indicated when comparing the Murnaghan equation with X-ray diffraction data.     

Valence and core state modifications in Pt3Ti

XPS data for the valence band, the Pt 4? states, and the Ti 2p states are presented for the intermetallic Pt₃Ti. Relative to the Pt valence band, the Pt₃Ti band shows a decrease in the density of states just below the Fermi level and a shift of the centroid to higher (binding) energy. Ti 2p and Pt 4? binding energies showed relatively large shifts with respect to the pure metals. These changes in the valence band density of states and core level binding energies are interpreted as arising from hybridization of the d-orbitals in both metals to form strong intermetallic bonds.     

Heats of formation of 3d and 4d transition metal hydrides

One electron energy spectra are used to explain the heats of formation of stoichiometric transition metal hydrides across the 3d and 4d rows. The trends agree reasonably with existing experimental information. The magnitudes are predominantly (but not exclusively) determined by the formation of a metal-H bonding band. In contrast to the screened proton model, the result is not directly related to the Fermi level density of states.     

Hydrogen-induced states in VHx and VDx observed by soft X-ray emission spectroscopy

From measurements of soft X-ray emission spectra (V-L₃) of VH_x and VD_x, a gradual change of d-band of V metal with addition of H(D), and an appearance of H(D)-induced states immediately below the d-band, are clearly demonstrated. The states, located at 7 eV below the Fermi energy for all compositions, are interpreted as being bonding states formed by H(D)-1s and V-3d orbitals. No isotope effects were detected within the accuracy of the experiment.     

Electronic band structures of the NbC—NbN alloy system from the X-ray photoelectron spectroscopic measurement

The energy distribution curves (EDC's) of valence band of NbC—NbN system have been measured by X-ray photoelectron spectroscopy. The characteristic features of the EDC's are well interpreted by the super-position of the densities of states of NbC and NbN in proportion to their concentration. Each band of NbC and NbN remains rigid and self-asserting in the band structures of NbC_xN_1-x alloy system.     

Symmetrical metallic and magnetic edge states of nanoribbon from semiconductive monolayer PtS2

Transition metal dichalcogenides (TMD) MoS₂ or graphene could be designed to metallic nanoribbons, which always have only one edge show metallic properties due to symmetric protection. In present work, a nanoribbon with two parallel metallic and magnetic edges was designed from a noble TMD PtS₂ by employing first-principles calculations based on density functional theory (DFT). Edge energy, bonding charge density, band structure, density of states (DOS) and simulated scanning tunneling microscopy (STM) of four possible edge states of monolayer semiconductive PtS₂ were systematically studied. Detailed calculations show that only Pt-terminated edge state among four edge states was relatively stable, metallic and magnetic. Those metallic and magnetic properties mainly contributed from 5d orbits of Pt atoms located at edges. What's more, two of those central symmetric edges coexist in one zigzag nanoribbon, which providing two atomic metallic wires thus may have promising application for the realization of quantum effects, such as Aharanov–Bohm effect and atomic power transmission lines in single nanoribbon.     

Photoemission studies of single crystals of titanium carbide

The electron distribution in the valence band from single crystals of titanium carbide has been studied by photoelectron spectroscopy with photon energies h?ω = 16.8, 21.2, 40.8 and 1486.6 eV. The most conspicious feature of the electron distribution curves for TiC is a hybridization between the titanium 3d and carbon 2p states at ca. 3–4-eV binding energy, and a single carbon 2s band at ca. 10 eV. By taking into account the strong symmetry and energy dependence of the photoionization crosssections, as well as the surface sensitivity, we have identified strong emission from a carbon 2p band at ? 2.9-eV energy. Our results are compared with several recent energy band structure calculations and other experimental data. Results from pure titanium, which have been used for reference purposes, are also presented.The valence band from single crystals of titanium carbide have been studied by means of photoelectron spectroscopy, with photon energies ranging from 16.8 to 1486.6 eV.By taking into account effects such as the symmetry and energy dependence of the photoionization cross-sections and surface sensitivity, we have found the valence band of titanium carbide to consist of two peaks. The upper part of the valence band at 3–4 eV below the Fermi level consists of a hybridization between Ti 3d and C 2p states. The C 2p states observed in our spectra were mainly excited from a band about 2.9 eV below the Fermi level. The APW^5–9, MAPW¹⁰ and EPM¹¹ band structure calculations predict a flat band of p-character between the symmetry points X′₄ and K₃, most likely responsible for the majority of C 2p excitations observed. The C 2s states, on the other hand, form a single band centered around ?10.4 eV.The results obtained are consistent with several recent energy band structure calculations^{5–11, 13} that predict a combined bonding of covalent, ionic and metallic nature.     

X-ray and UV photoelectron spectra of the oxides NbO2, MoO2 and RuO2

HeI and Mg Kα_1,2 valence band photoelectron spectra of polycrystalline samples of NbO₂, MoO₂ and RuO₂ are reported. A marked increase is observed in the intensity of the metal 4d structure, relative to that due to oxygen 2p electrons, on changing from X-ray to UV excitation. The superior resolution of the 4d signals in the HeI spectra reveals the presence of the Fermi edge in the metallic oxides MoO₂ and RuO₂. In addition, the HeI spectrum of MoO₂ shows a splitting of the metal 4d signal, confirming established ideas concerning the electronic structure of such materials.     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

On the fermi velocity and static conductivity of epitaxial graphene

The models of the energy density of states of a metallic or semiconductor substrate, which does not further lead to divergences, have been proposed to calculate the characteristics of epitaxial graphene. The Fermi velocity of epitaxial graphene formed on a metal has been shown to be greater than that in free-standing graphene irrespective of the position of the Fermi level. On the contrary, the Fermi velocity of graphene formed on a semiconductor is lower so that the lower is the Fermi velocity, the closer is the Fermi level to the center of the band gap of the semiconductor. The zero-temperature static conductivity σ of epitaxial graphene has been calculated according to the Kubo-Greenwood formula. The quantity σ_m of undoped graphene on metal has been shown to decrease with an increase in the deviation of the Dirac point ?_D (which coincides with the Fermi level of the system) from the center of the conduction band of the substrate. In the case of the semiconductor substrate, the static conductivity σ_sc turns out to be nonzero and amounts to σ_sc = 2e ²/π?-only under the condition ?_F =?′_D, where ?′_D is the Dirac-point energy renormalized by the interaction with the substrate.     

Structure electronique des oxydes de cobalt CoO et Co3O4

The total density of occupied states in the valence band of CoO and Co₃O₄ is determined by XPS and UPS. From variations of excitation probability of the bands, the 4 e V wide O2_p band is shown to be located around 5 eV for both oxides, while structures obtained from photoionisation of the localized 3d band spread over 10 eV range below the Fermi level overlapping with O2_p band. The 3d peaks located at binding energy <3 eV correspond to the calculated energy of the d_n ?1 manifold final state in the octahedral and tetrahedral crystal field of CoO and Co₃O₄. The 3d levels at higher binding energy are shown to occur from configuration interaction in both final and initial states. These last peaks are higher in intensity for CoO relative to Co₃O₄. A superior limit for the width of the 3d initial band in a one electron energy diagram is given to be <3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV from shake-up and Auger energy confirms the Mott insulator nature of CoO.     

The study of the energy band structures of TiC,VC, Ti4C3 and V4C3 by the LMTO-ASA method

The energy band structures of TiC, VC, Ti₄C₃ and V₄C₃ have been studied by the linear muffin-tin-orbital method (LMTO). The influence of vacancies on the density of states (DOS) in the 2s C-band is a uniform reduction and a narrowing of this DOS. The splitting of the peak in the low-energy part of the 2p C, 3d Me-band (Me = Ti, V) is observed, while in the neighbourhood of the Fermi energy two peaks of DOS appear which consist of 3d Me- and vacancy states. Under the influence of vacancies the electronic charge in the carbon atomic sphere is shifted partly into the vacancy sphere. For Ti₄C₃, the increase of the Fermi energy and DOS at this energy is observed, while in the case of V₄C₃ these values decrease. In the presence of vacancies a contraction of crystal lattice is observed while the bulk moduli of TiC and VC diminish which is most pronounced for VC. The results are compared with previous data obtained by the LCAO coherent potential and APW calculations and with the experimental data concerning the DOS at the Fermi energy.