Calculation of chemisorption energies of oxygen on narrow-gap semiconductors

Newns' self-consistent model for hydrogen chemisorption on transition metals is extended to calculate the chemisorption energy ΔE of oxygen on Si, Ge and III–V compounds. ΔE is found to depend on the widths of the energy gap and valence band, the crystal work function and the crystal plane, |ΔE₍₁₀₀₎|>|ΔE₍₁₁₁₎|. In general, larger ΔE's are associated with wider energy gaps.     

Optical studies of (NH4)2SO4 single crystal in the paraelectric phase

Transmittance and absorbance spectra of (NH₄)₂SO₄ single crystals along [010] direction were measured at different temperatures (296, 308, 318, 328 and 348 K) in the paraelectric phase. The absorption coefficient was computed and the analysis of the data revealed the existence of two optical transitions in (NH₄)₂SO₄ single crystals. The direct and indirect band gaps were shifted towards the longer wavelength with increasing temperature. The data on the allowed indirect transition was analyzed and interpreted in terms of two valence bands originated by spin orbit interaction and crystal field splitting. The momenta E_p were calculated as the difference between E_g1, the first valence to conduction band, and E_g2 for the second valence band at different temperatures. The results of extinction coefficient (k), the refractive index (n), and dielectric constants (ε) were also discussed and calculated as a function of wave length (λ). The heat treatment of the crystals proved that the variations of these optical parameters can be consequence of the internal microstructure changes caused by annealing.     

Neutron scattering study of phonons associated with indirect band-gap transition in AgBr

Phonons in AgBr are studied by neutron inelastic scattering along the [111] direction of reciprocal lattice. From the phonon dispersion and the optical data, it is concluded that the valence band maximum is at the L-point and the phonons participating in the indirect band-gap transition are identified as TO(L) and LA(L).     

Generalized susceptibilities and phonon anomalies in Pd and Pt metals

The generalized susceptibility, χ(q), in Pd and Pt for q along the [100], [110], [111], and [120] directions was determined from their APW and RAPW energy band structures, respectively, using the analytic tetrahedron linear energy scheme of Rath and Freeman. The band structures were previously found to yield Fermi surface radii, temperature dependencies of the static magnetic susceptibility, χ(T), resistivity, and a spin lattice relaxation, T₁T, in very good agreement with experiment. In the χ(q) calculations, we used 2048 tetrahedra in 1/48th irreducible BZ and the energy eigenvalues for bands 4, 5, and 6 which cross the Fermi energy as fitted to a Fourier series representation. The intraband parts of χ(q) at q = 0 for both metals are found to agree with the density of states at the Fermi energy to without 0.5%. Our results show that the dominant contribution to χ_intra arises from the dominant band 5 whose “jungle-gym” FS has strong nesting features; the main peak for Pd occurs at the same q value (= 0.65π/a) for q along the [0q0], [q, q, 0], and [q, q, q] directions. The locus of this main peak is a square in the (0, 0, 1) plane. The maximum of χ_intra for q along the [110] and [111] directions are 23% and 13%, respectively, higher than the value of χ(q) at q = 0. For q along the [010] and [120] directions, the peak is, however, lower than the value of χ_intra at q = 0. Hence, while phonon anomalies are predicted for the [110] and [111] directions, no anomaly is predicted for either the [100] or [120] direction. The predicted q value for the [110] anomaly, $\text{q}\text{= 0.65π/a}$ is close to the experimental value of ～0.7 π/a. Although there may be a hint of an anomaly at 0.56 [111] in the measurements, a more detailed investigation of this region is called for. For platinum, χ_intra for q along the [010], [110] and [111] directions has main peaks which occur at q = 0.68 π/a, 0.75 π/a, and 0.85 π/a, respectively. Here too, this main peak comes from the nesting of the jungle-gym Fermi surface which is not, however, as flat as that of palladium. Anomalies are predicted (although weaker in Pt than in Pd) along [110] and [111] but not along [100] and [120]. The [110] anomaly is close to the measured q value (～0.7–0.8 π/a). Also in agreement with experiment, we predict a weaker [110] anomaly for Pt than for Pd. In both Pd and Pt, weaker anomalies are predicted for the [111] direction than for the [110] direction.     

Comparison of the calculated electronic structures of [111] and [001] GaAs/AℓxGa1-xAs semiconductor superlattices

A theoretical comparison of the electronic structures of long-period (about 300 Å) N_GaAs×N_AℓGaAs GaAs/Aℓ_0.3Ga_0.7As superlattices grown along the [111] direction and superlattices grown along the [001] direction is presented. Almost all qualitative features of the theoretical results are in good agreement with experiments by Hayakawa et al. The observed optical transition enhancement in the [111]-oriented quantum-well structures is caused by the topological difference in the superlattices, and is only partly due to the fact that the heavy holes in the [111] superlattices have larger transverse effective masses, and therefore have larger two-dimensional valence band densities of states.     

Angle-resolved photoemission and valence band dispersions for GaAs: Direct vs indirect models

Angle-resolved photoemission measurements for GaAs(110) have been extended to hv= 100 eV. These results show that dominant emission peaks are due to direct transitions. Weaker one-dimensional density of states features sometimes observed are due to surface umklapp/secondary cone and lifetime effects. Accurate band dispersions

for all four valence bands GaAs along the [110] direction are given using simple normal emission and off-normal emission methods. Electron and hole lifetimes are directly determined.     

Structural considerations on the mechanism of the shock-induced zircon-scheelite transition in ZrSiO4

The crystal structure of the scheelite-type ZrSiO₄, which was transformed from the zircon-type under shock compression, was studied using an X-ray powder diffraction analysis. Positional parameters of O^2- in the 16f site are determined to be u = 0.28, v = 0.14 and w = 0.07 (space group, I4₁/a). The X-ray powder diffraction lines were broad, indicating that the scheelite-type ZrSiO₄ has considerable residual strain in the crystal. The mechanism of this shock-induced phase transition is discussed in terms of the displacive mechanism, where the [110] direction of the zircon-type is converted to the [001] direction of the scheelite-type. This model can explain why this zircon-scheelite transition occurs so fast under shock compression.     

Spatial-dispersion induced birefringence in cubic crystals: CuBr and CuI

A natural birefringence in single crystals of copper halides is observed and measured in the exciton part of the spectrum. This intrinsic birefringence is due to the spatial dispersion of the dielectric constant ?(ω, q). Its spectral dependence and strong enhancement near the energy gap can be explained only, if we take account of the strong excitonic contribution in these compounds. This effect is related to the valence band anisotropy (warning) and thus allows a direct determination of the Luttinger band parameters | γ₂ - γ₃ | for these compounds.     

Band discontinuity in GaAs/AlAs superlattices with InAs strained insertion-layers

We have theoretically investigated the valence-band discontinuity (ΔE_v) at the (100) GaAs/AlAs interface with the InAs strained insertion-layer. The theoretical calculation is carried out by the self-consistent tight-binding method with the sp³s* basis in the (GaAs)₅/(InAs)₁/(AlAs)₅/(InAs)₁ [100] superlattice. ΔEv at the GaAs/InAs(1ML)/AlAs interface is calculated to be 0.50 eV, which is practically equal to ΔEv = 0.51 eV at the GaAs/AlAs interface with no InAs layers. The insertion of the InAs monolayer changes the detail of valence charge density at the GaAs/AlAs interface but does not change ΔE_v. The result of calculation is in consistent with our experimental measurement by using the x-ray photoelectron spectroscopy.     

Ab initio calculations of band structure and thermophysical properties for SnS2 and SnSe2

The electronic band structure and elastic constants of SnS₂ and SnSe₂ have been calculated by using density-functional theory (DFT). The calculated band structures show that SnS₂ and SnSe₂ are both indirect band gap semiconductors. The upper valence bands originate mainly from S_p and Sn_d electrons, while the lowest conduction bands are mainly from (S, Se) _p and Sn_s states. The calculated elastic constants indicate that the bonding strength along the [100] and [010] direction is stronger than that along the [001] direction and the shear elastic properties of the (010) plane are anisotropic for SnS₂ and SnSe₂. Both compounds exhibit brittle behavior due to their low B/G ratio. Relationships among volumes, the heat capacity, thermal expansion coefficients, entropy, vibrational energy, internal energy, Gibbs energy and temperature at various pressures are also calculated by using the Debye mode in this work.     

Scattering of electrons due to screw dislocations

The phase dismatching effect on the scattering due to screw dislocations is reformulated to take the discreteness of lattice sites into account. Thet-matrix for an electron scattered from the statep top′ is $$\begin{gathered} t\left( {p,p'} \right) = ip_z T\exp \left\{ {i\left( {p - p'} \right) \cdot m_A } \right\}\exp \left\{ {i\left( {p - p'} \right) \cdot \left( {i + j} \right)/2} \right\} \hfill \\ \cdot \frac{{\left[ {\exp \left( { - ip_y } \right) - \exp \left( {ip'_y } \right)} \right] + \left( {\upsilon _y /\upsilon _x } \right)\left[ {\exp \left( {ip_x } \right) - \exp \left( { - ip'_x } \right)} \right]}}{{1 - \exp \left[ {i\left\{ {\left( {p_x - p'_x } \right) + \left( {\upsilon _y /\upsilon _x } \right)\left( {p_y - p'_y } \right)} \right\}} \right]}} \hfill \\ \end{gathered}$$ for 0≦v _y ≦v _x ≦1 and |p _y |, |p′ _y |?1. Here,v is the group velocity of the incident electron andm _A is the position of the dislocation axis. All vector notations represent vectors in two-dimensional space, the unit vectors of which are represented byi andj. Expressions for |p _y |, |p′ _y |?π and other values ofv are obtained through simple modifications. As an application, the resistivity due to screw dislocations is discussed qualitatively.     

Simultaneous Analysis of Rovibrational and Rotational Spectra of thev5= 1 andv8= 1 Vibrational Levels of Propyne

The microwave and submillimeter wave spectra of propyne between 17 and 358 GHz were measured and the rotational transitions in thev₈= 1 excited vibrational state of the CH₃rocking vibration were assigned. About 1050 wavenumbers of the ν₈vibration–rotation fundamental band and about 600 wavenumbers of the ν₅fundamental band of the[formula]stretching vibration were assigned from the infrared spectrum between 910 and 1130 cm⁻¹which was used previously (G. Graneret al., J. Mol. Spectrosc.161,80–101 (1993)) in the analysis of the combinationv₉=v₁₀= 1 and thev₁₀= 3 overtone levels (ν₉being the[formula]bending and ν₁₀the[formula]bending vibrations). The rovibrational and rotational data corresponding to the two fundamental levels were analyzed simultaneously in least-squares fits using a model which treats together all the vibrational levels in the region around 1000 cm⁻¹with their strong anharmonic and vibration–rotation resonances. The refined parameters reproduce the infrared and submillimeter wave data of thev₅= 1 level with standard deviations of 0.32 × 10⁻³cm⁻¹and 59 kHz, respectively, while for thev₈= 1 level the standard deviations were 0.41 × 10⁻³cm and 290 kHz. The refined parameters of the combination and overtone levels provide reliable predictions for future submillimeter wave studies.     

Electronic band structure of partially inverse spinel MgIn2S4 as calculated by the semiempirical pseudopotential method

The electronic band structure of the partially inverse spinel MgIn₂S₄ has been calculated on the symmetry lines ΓΛL, ΓΔX and ΓΣK by the semiempirical pseudopotential method. The general features of the band structure of MgIn₂S₄ are quite similar to those of the normal spinel CdIn₂S₄. The conduction band minimum is located at Γ and the valence band maximum is along the Σ line. The indirect energy gap (Γ_1cΣ_4v) is 2.50 eV. The effects of magnesium vacancy and variations in the cation distribution and in the parameter u are examined and shown to be small.     

Phonon dispersion in AgBr and exchange of the transverse mode Eigenvectors at L

Using inelastic neutron scattering, phonon dispersion curves for AgBr at 85 K are measured along the 〈100〉, 〈110〉 and 〈111〉 directions in reciprocal lattice. Special attention is payed to the anomalous behaviour of the TA and TO branches at the L-point (0.5; 0.5; 0.5). With high resolution (Δv = 0.24 THz) their frequencies are determined to be 1.54 and 1.93 THz, respectively. The ratio of their integrated intensities is found to be 2.15 ± 0.4. This value is in good agreement with the ratio of 2.38 calculated under the assumption that at L the heavier (Ag⁺) ions is vibrating with the higher and the lighter (Br^-) ion with the lower frequency, as suggested by recent lattice dynamical calculations. Comparison of our phonon frequencies with corresponding optical data prove that the momentum-conserving phonons associated with the lowest indirect exciton transition belong to the TO and LA phonon branches at L. Since the lowest conduction band minimum at Γ is well established experimentally, our results in turn imply that the uppermost valence band maximum is right at the L-point.     

23Na NMR study of the local order in the Na1/2Bi1/2TiO3 structure in a weak magnetic field

The orientation dependences of the second-order quadrupole shifts of the central component in the ²³Na NMR spectrum were studied in the temperature range 293–760 K. The profile of the spectral distribution is calculated using various models of the Na_1/2Bi_1/2TiO₃ structure. The calculations agree with the experimental data for the monoclinic structure of a polar cluster with two Na displacement components: a displacement along the [111] _p direction and a small displacement statistically or dynamically disordered over six equally probable [100] _p -type directions. Tetragonal-phase nuclei and monoclinic clusters with a very small displacement component along the [111] _p direction are found to coexist and have close energies over the temperature range 580–610 K. The results obtained provide new information concerning the character of the diffuse phase transition at 610 K.     

Effect of interband scattering on kinetic coefficients and estimates of the parameters of the band spectrum of Sb2Te3

It has been shown that uncertainties in the interpretation of experimental data on transport phenomena in Sb₂Te₃ are resolved in the two-band model with the consistent inclusion of the interband hole scattering. The performed calculation is in quantitative agreement with the experimental data in the temperature range from 77 to 400 K for the following parameters of the band spectrum: the effective mass of the density of states of light holes m _d1 ≈ 0.6m ₀ (where m ₀ is the free electron mass), the effective mass of the density of states of heavy holes m _d2 ≈ 1.8m ₀, and the energy gap between nonequivalent extrema of the valence band ΔE _v(T) ≈ 0.15–2.5 × 10^?4 T eV.     

Investigation of electronic structure of Nd-doped TiO2 nanoparticles using synchrotron radiation photoelectron spectroscopy

Doping with transition metal ions in TiO₂ has been found effective to modify the electronic structure of TiO₂ nanoparticles. Application of synchrotron radiation photoelectron spectroscopy (SRPES) to Nd-doped TiO₂ nanoparticles revealed that there existed different peak positions and structure with different doping concentration in the valence band spectra. From the onset of valence band spectrum, it was observed that doping Nd ions alters the electronic structure and makes the band gap of TiO₂ narrow.     

Theoretical studies of ground and excited states in a series of Zn(II) complexes,derived from thiourea and thiosemicarbazide

Theoretical studies for a series of mono- and binuclear zinc (II) complexes Zn(CH₃COO)₂(H₂L)₂ [H₂L = N-2-propenyl-N ^′-2-pyridinylthiourea] (A), Zn₂(CH₃COO)₂(H₃L-a)₂ [H₃L-a = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-phenylcarbothioamide] (B), and Zn(H₃L-b)₂ [H₃L-b = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-(2-propenyl)carbothioamide] (C) have been performed on their structures and excited-state absorption spectra. The singlet ground-state geometries are fully optimised at three DFT levels, i.e., B3LYP, B3PW91, and M06. Different geometries, i.e., strongly distorted tetrahedral coordination environment in complex A, distorted square-pyramidal environment in complex B, and irregular octahedral mode in complex C are identified. Consequently, the spectroscopic properties are calculated by means of time-dependent density functional theory (TDDFT) with the Polarisable Continuum Model (PCM) based on the optimised gas-phase geometries. Three absorption peaks are identified for every complex, which are in good agreement with the experimental ones. For complex A, all three absorption peaks centered at 280.33 nm, 268.09 nm, and 250.87 nm, respectively, are ascribed to the (p,π) → π* transition with a mixed intraligand charge-transfer (ILCT)/ligand-ligand charge-transfer (LLCT) character. The composition of frontier orbitals involved in major absorption bands for the three complexes shows similarities, which results in the almost homologous transition attributions and characteristics. A remarkable bathochromic shift in the lowest-lying absorption band is observed for complexes B and C as compared with complex A, which is attributed to the decreased H (HOMO)-L (LUMO) energy gap (ΔE |HOMO-LUMO|) by the formation of conjugate metallocycles in complexes B and C.     

Spectral dependence of erythrocyte response to low-intensity irradiation at 570–590 nm

Red blood cells irradiated with copper laser pumped by a dye laser exhibit a photoresponse whose spectral dependence corresponds to the molecular oxygen absorption band [2³Σ _g ^? →¹Δ _g (v=0)+¹Δ _g (v=1)].     

The permanent electric dipole moment of holmium monoxide, HoO

The high resolution molecular beam laser-induced fluorescence (LIF) spectrum of the (0, 0) band of the [17.6]7.5-X₁8.5 system of holmium monoxide, HoO, has been recorded field free and in the presence of a variable static electric field. The rotational constant, B₀, and magnetic hyperfine structure constant, h, for the v = 0 levels of the [17.6]7.5 and X₁8.5 states were obtained by assigning and fitting the field-free spectral features. The Stark shifts and splittings in the LIF spectra were analyzed to produce values for the magnitude of the permanent electric dipole moments, |μ|, of 3.96(6) and 4.80(5) D for [17.6]7.5, v = 0 and X₁8.5, v = 0, respectively.