Edge-modified zigzag-shaped graphene nanoribbons: Structure and electronic properties

Control of the band gap of graphene nanoribbons is an important problem for the fabrication of effective radiation detectors and transducers operating in different frequency ranges. The periodic edge-modified zigzag-shaped graphene nanoribbon (GNR) provides two additional parameters for controlling the band gap of these structures, i.e., two GNR arms. The dependence of the band gap E _g on these parameters is investigated using the π-electron tight-binding method. For the considered nanoribbons, oscillations of the band gap E _g as a function of the nanoribbon width are observed not only in the case of armchair-edge graphene nanoribbons (as for conventional graphene nanoribbons) but also for zigzag GNR edges. It is shown that the change in the band gap E _g due to the variation in the length of one GNR arm is several times smaller than that due to the variation in the nanoribbon width, which provides the possibility for a smooth tuning of the band gap in the energy spectrum of the considered graphene nanoribbons.     

Structural properties and band structure of heavy fermion systems: CeCu2Si2 and LaCu2Si2

The structure of CeCu₂Si₂, isotypic with ThCr₂Si₂, has been refined in a single-crystal study. The atomic parameters were used in self-consistent LMTO band structure calculations for CeCu₂Si₂ and isostructural LaCu₂Si₂. The results are analysed in terms of energy levels, charge distribution and in particular Fermi surface properties. The Ce-4f levels are situated mainly aboveE _F , except near the Γ-point. The density-of-states atE _F is large and heavily concentrated around the Ce-4f band. This makes local Ce 4f fluctuations possible, while interaction with the rest of the band structure is small. The comparison with LaCu₂Si₂ shows that the additional Cef electron is partly promoted into the non-f bands. Large enhancement factors are required to bring band results into agreement with observed specific heat and magnetic critical field. Strong Fermi surface anisotropies are pointed out for both compounds suggesting new experiments on single crystals.     

Electronic structure of UPd3 — A localized f compound

Various experiments on UPd₃, the analogue of the heavy fermion superconductor, UPt₃, have ascertained that there are two f electrons per U which are localized in a magnetic singlet state. Recently, both photoemission (PES) and de Haas-van Alphen (dHvA) experiments have been reported on UPd₃. To complement this experimental work, local density energy band calculations have been performed on UPd₃ where the f electrons have been treated as core states. The resulting density of states is found to be in good agreement with photoemission data. The theoretical Fermi surface is found to be more complex than current dHvA data indicate, but one can still unambiguously assign theoretical extremal orbits to the experimental data. Thus again, the data is consistent with a local f² configuration. Since the band calculations can explain the dHvA data in heavy fermion UPt₃ with the f electrons treated as band states, one finds that the Kohn-Sham ansatz for treating the f electrons as Bloch states breaks down between these two cases. This finding is confirmed by recent U(Pd_xPt_3-x) alloy experiments which show a sudden decrease in the specific heat coefficient when alloying these two compounds.     

On the specific features and transformation of the band structure of mercury-based HTSC compounds

A systematic analysis of the temperature dependences of the thermopower S(T) for different phases of the HgBa₂Ca _n?1Cu _n O_2n+2+δ family (n=1, 2, 3) at different doping levels is performed in the framework of a narrow-band phenomenological model. Quantitative estimates of the main parameters of the band responsible for conduction in the normal phase of HgBa₂Ca _n?1Cu _n O_2n+2+δ are given for optimally doped samples. The character of the variation in these parameters with an increasing number n of the copper-oxygen layers is discussed. A trend toward broadening of the conduction band with increasing n is revealed, which can be due to the increase of the density-of-states (DOS) peak near the Fermi level with an increasing number of the CuO₂ layers responsible for the formation of the conduction band. It is found that an increase in the number n leads to an increase in the fraction of localized carriers in the band owing to a more defective structure observed in the more complex phases of HgBa₂Ca _n?1Cu _n O_2n+2+δ. The variations in the band-structure parameters in going from under-to overdoped compositions in the HgBa₂Ca _n?1Cu _n O_2n+2+δ family are also discussed.     

Collisional parameters of H2O lines: Velocity effects on the line-shape

This paper is devoted to the effects of velocity on the shapes of six R(J) lines of the ν₃ band of water vapor diluted in N₂. The experiments have been made at room temperature for total pressures between 0.1 and 1.2 atm using a tunable infrared laser frequency difference spectrometer. These measurements, which study broad and narrow lines of low and high J values, are first analyzed using the Voigt and the hard collision (HC) model. It is shown that both lead to unsatisfactory results, the Voigt profile being unable to account for the line narrowing whereas the friction (narrowing) parameter deduced using the HC approach has an unphysical dependence on pressure. Furthermore, at elevated pressure where Dicke narrowing and Doppler effects are negligible, deviations between experimental and fitted profiles are still observed, indicating inhomogeneous effects due to the speed dependence of collisional parameters. In order to go further, an approach based on the kinetic impact equation accounting for both the Dicke narrowing and the speed dependence has been applied. It uses velocity-dependent broadening and shifting coefficients calculated with a semi-classical approach and two parameters. The latter, which govern the memory functions of the modulus and orientation of the H₂O velocity are considered as free parameters and determined from experiments. The results show that all profiles, regardless of pressure and of the transition, can be correctly modeled using a single set of memory parameters. This demonstrates the consistency of the approach, which is then used to analyze the different regimes that monitor velocity effects on the line profile.     

Measured and predicted band model parameters of BF3(v3) at high temperatures

Two experimental techniques were used to determine the high temperature infrared absorption coefficients of the v₃ band of BF₃. A high temperature flow tube fitted with a multipass infrared absorption cell was used to determine the BF₃ absorption coefficients at 295, 585, 870, 1150, and 1440K. BF₃ was also used in a flame emission-absorption apparatus to determine the BF₃ absorption coefficients at 2400 K.A generalized formulation for predicting the S/d and 1/d band model parameters of symmetric top perpendicular bands of MX₃ molecules is presented. The effect of including nuclear spin statistics in computing the S/d and 1/d band model parameters is considered. It is shown that nuclear spin statistic?s effect only the 1/d parameter and are significant only for the case of zero nuclear spin. A number of practical considerations, which arise in designing a computer algorithm to calculate the S/d and 1/d parameters, are discussed.Comparisons of the theoretical and experimental BF₃ absorption coefficients are made. Good agreement between theory and experiment at all temperatures was obtained by adjusting only two vibrational energy coupling constants, _χ23 and _χ34. Predicted S/d and 1/d band model parameters at 300, 600, 900, 1200, 1500, 2000, 2500, and 3000 K are presented.     

V centers in single crystal Al2O3

From optical and thermal bleaching experiments it is concluded that the 400 nm absorption band which appears in Al₂O₃ after γ-irradiation is a composite V band. One of its components is attributed to the V^-_OH center which also is responsible for a localized vibrational band at 3316 cm^-11 analogous to the one observed for the V_OH center in MgO. The irradiation also results in electron trapping at Cr³⁺ impurity ions to produce a band at 227 nm. Annealing at 170°C destroys the V^-_OH center by releasing holes which convert the Cr²⁺ to Cr³⁺ with an attendant thermoluminescence.     

Reflectance spectra and photonic band gaps of a one-dimensional photonic crystal based on a silicon-air periodic structure

The reflectance spectra of a one-dimensional photonic crystal based on a silicon-air periodic structure are calculated. A map of photonic band gaps is plotted, which makes it possible to deliberately choose the geometric parameters of the structure (the thickness of silicon partitions D _Si and the period A) for different ranges of the wavelength λ. To obtain structures with a photonic band gap in the range A/λ=0.15–0.5, the main region (as rule, corresponding to the lowest frequencies) can be used, and, taking into account the secondary photonic band gaps, the range A/λ can be extended to 1 and even more. In addition, it is found that, in the range D _Si/A=0.4–0.9, the secondary band gaps may be wider than the main ones (on the frequency scale). The influence of the filling factor D _Si/A on the formation of the edges of spectral bands is revealed.     

Assignment of submillimeter laser lines in methyl chloride

Assignments are proposed here for 19 far infrared laser lines in CH₃Cl excited by a CO₂ laser and for the CH₃Cl transitions which are pumped. In each case the chlorine isotopic species involved is determined. In addition, a complete set of band parameters is obtained for the ν₆ band of CH₃³⁷Cl as well as for CH₃³⁵Cl. The vibrational isotopic shift Δν(35–37) is found to be 0.386 cm^?1 for the ν₆ band of CH₃Cl.     

Elastic, electronic, and optical properties of hypothetical SnNNi3 and CuNNi3 in comparison with superconducting ZnNNi3

The elastic, electronic, and optical properties of MNNi₃ (M=Zn, Sn, and Cu) have been calculated using the plane-wave ultrasoft pseudopotential technique, which is based on the first-principle density functional theory (DFT) with generalized gradient approximation (GGA). The optimized lattice parameters, independent elastic constants (C₁₁, C₁₂, and C₄₄), bulk modulus B, compressibility K, shear modulus G, and Poisson's ratio υ, as well as the band structures, total and atom projected densities of states and finally the optical properties of MNNi₃ have been evaluated and discussed. The electronic band structures of the two hypothetical compounds show metallic behavior just like the superconducting ZnNNi₃. Using band structures, the origin of features that appear in different optical properties of all the three compounds has been discussed. The large reflectivity of the predicted compounds in the low energy region might be useful in good candidate materials for coating to avoid solar heating.     

Valence band structure of fractional Wannier-Stark effect shallow InGaAs/InGaAs superlattices

Strain induced effects on the valence band structure of In_xGa_1-xAS/In_yGA_1-yAs (x ≈ 0.47, y ≈ 0.6) shallow superlattices are analyzed by optical spectroscopy. The formation of minibands and the spatially indirect nature of the electron-light-hole transition are observed by photocurrent experiments. Field induced spectral changes of the photocurrent spectra are attributed to Wannier-Stark localization. Heavy hole related fan diagrams are derived for all samples. In contrast, the electron-light-hole Wannier-Stark ladder appears to be very sensitive to material parameters. These results are compared with theoretical calculations of the excitonic absorption coefficient.     

Valence band photoemission spectroscopy of a ternary layered semiconductor: ZnIn2S4

UV photoemission spectroscopy (UPS) experiments have been carried out on the layer compound ZnIn₂S₄ employing several different photon energies in the range $\text{h}\text{?}{}_{\mathrm{\omega }}\text{= 9.5?21.2}\text{eV}$. The energy distribution curves (EDC's) exhibit four valence band density of states structures besides the Zn 3d peak. These five peaks appear 0.90 eV, 1.6 eV, 4.3 eV, 5.8 eV and 8.7 eV respectively below the top of the valence band, E_v. The atomic orbital character of the shallowest peak A appears different from that of the three deeper valence band peaks B, C and D and this is discussed in terms of the more or less pronounced ionic character of the intralayer chemical bonds. These results demonstrate that an overall understanding of the electronic states in complex structures can be achieved by an approach based on photoemission experiments and chemical bonding considerations which has been widely used in the past to study simple binary layer compounds.     

Effect of lattice constant on band-gap energy and optimization and stabilization of high-temperature In x Ga1?x N quantum-dot lasers

We analyze the effect of the lattice constant on the band-gap energy of In _x Ga_1?x N and optimize the structure of the device with a separate-confinement heterostructure. To vary the lattice constants, we change the In molar fraction, which permits us to investigate a wide range of the band gap of the active material employed in diode lasers. In _x Ga_1?x N is a promising active material for high-performance 1.55???m quantum-dot lasers due to its excellent band-gap-energy stability with respect to temperature variations. The band gap of In _x Ga_1?x N decreases from 3.4 to 0.7?eV, and the necessary band gap can be achieved by changing the lattice parameters depending on the device application. It has been found that In_0.86Ga_0.14N can be a promising material for emitting light at a wavelength of 1.55???m.     

Optical absorption due to transitions between bands and local levels in CdCr2Se4

The theory of optical absorption due to transitions between a valence band and a hydrogen-like local level associated with a conduction band is modified to permit an arbitrary power-law dependence of energy on the magnitude of the wave-vector of carriers in the valence band. The observed absorption for photon energies below 1.6 eV in the ferromagnetic semiconductor CdCr₂Se₄ is discussed in terms of a combination of two types of terms. The first type of absorption is due to transitions to a local level from a band with two branches, in each of which there is an energy region with a width of 0.28 eV or more beginning 0.10–0.16 eV from the band edge, in which the energy measured from some origin near but not necessarily equal to the band-edge is approximately proportional to (wave-vector)^{($\text{1}\text{3}$)}. The second type of absorption has a dependence on photon energy ?ω of the form (?ω ? E₃)², where E₃ is a threshold energy probably connected with indirect transitions between bands as suggested by Sakai, Sugano and Okabe. After constraints on parameters appearing in the theory are imposed by use of results of these authors and of Shepherd, it is found that curves of Harbeke and Lehmann on optical absorption in CdCr₂Se₄ at 4.2, 78, 130 and 298 K in the photon-energy range 1.14–1.42 eV can be fitted to a mean accuracy of 3%, using an average of 3.75 adjustable parameters for each curve. The strength of the indirect band-to-band absorption does not have the temperature dependence expected for phonon-assisted indirect band-to-band transitions, but can be described by a term independent of temperature plus another term proportional to the square of the deviation of the magnetization from saturation. The fitting of the absorption curves requires that the ratio of the widths of the two branches of the bands varies from about 1.6 at low temperatures to 1.35 at 298 K and that the total width of the bands involved is less than 1 eV.     

The 2ν3 band of CH4 revisited with line mixing: Consequences for spectroscopy and atmospheric retrievals at 1.67 μm

This paper presents a study of absorption in N₂-broadened P and R manifolds of the 2ν₃ band of CH₄ near 6000 cm⁻¹ using high resolution laboratory and atmospheric spectra. This region is of prime importance for the retrieval of methane abundances in the Earth's atmosphere using ground-based or space-borne spectrometers. Recent laboratory investigations have been devoted to the methane spectroscopic parameters in this band, motivated by their previous poor knowledge and their increasing use by remote sensing experiments. In the absence of a better model, previous studies have used Voigt line shapes and thus purposely neglected line mixing (LM). In this paper, we first present direct comparisons between measured laboratory spectra and the results of a model which accounts for LM without adjusting any of the spectroscopic parameters. A good agreement is obtained and the results show that LM does have a significant influence on the shapes of P and R manifolds. Hence, most previously observed discrepancies were not due to improper broadening and shifting coefficients but to the neglect of this effect. This also confirms that widths and shifts derived in recent 2ν₃ band studies neglecting LM are “effective” and lack physical meaning, as suggested in a previous work [17] (Frankenberg et al., 2008). In a second step, the conclusions from the laboratory data are tested using ground-based atmospheric solar absorption spectra. The fit residuals obtained confirm the quality of the proposed model and evidence the impact of line mixing on CH₄ atmospheric spectra. The present results also confirm that laboratory and atmospheric spectra can alternatively be accurately modeled neglecting LM and using ad hoc broadening and shifting parameters. Conclusions of this exercise can be drawn from two perspectives. From the point of view of spectroscopy and understanding of processes, accurate line parameters will not be deduced from fits of laboratory measurements unless line-mixing effects are included in the spectral-shape model. In the meantime, and from the point of view of atmospheric retrievals, neglecting LM with suitable effective line parameters is convenient and accurate (within current retrieval uncertainties). Note that this is only true if this approach is not used for total pressures significantly above 1 atm (e.g. Jupiter).     

Band structure for some Nb3X compounds

The tight binding method is used to calculate band structure for a number of Nb₃X compounds. The 4d band of the niobium, as well as the s-p bands of the X-atoms, are considered. The transfer and overlap integrals are calculated using tabulated atomic orbitals. The crystal field parameters (CFP) are estimated more carefully, taking into account deviations from a muffin-tin potential. We employ here the independent band approximation in which no interband interaction is considered. This approximation has been proved successful for the V₃Ga case, and it is estimated here that interband interaction may shift some levels up or down by 50 mRy or so, but the overall band-structure does not change. The Fermi level is found to lie in the neighbourhood of three peaks; one belongs to the δ₂(d_xy) band and the two others belong to the π(d_xz, d_yz) band.     

Magnetic absorption of hexagonal crystals CdSe in strong and weak fields: Quasi-cubic approximation

The spectra of ultrathin free samples of hexagonal CdSe in a magnetic field up to 8 T are studied at 1.7 K. The fan-shaped diagram contains information on weak (the Zeeman effect and diamagnetic shift), as well as strong fields (transitions between Landau levels). As a result of the application of two theoretical models for combined interpretation of strong-and weak-field experimental data, two sets of (band and polaron) parameters are calculated for hexagonal CdSe in the quasi-cubic approximation. The values of the obtained polaron/band parameters are: the electron effective mass m _e =0.125/0.116m ₀, the Luttinger parameters γ₁=1.5/1.72, γ=0.29/0.37, κ=?0.63, and the effective electron g-factor g _e =0.7.     

Extended assignment and analysis of the ν2 and ν4 infrared bands of 12CH4

Infrared spectra of the ν₂ and ν₄ bands of ¹²CH₄ have been assigned up to J′ = 20 in the ν₄ band and J′ = 17 in the ν₂ band. Assignments are presented for over 1000 transitions ranging from 1123 to 1712 cm^?1, which involve 652 upper-state energy levels of the two bands. The 652 upper-state levels have been fitted with a weighted standard deviation of 0.0026 cm^?1, almost all levels being reproduced to within their experimental error, by a Hamiltonian for the coupled upper states containing 28 refining parameters and 4 fixed parameters. Calculated relative intensities are also tabulated and discussed in relation to recent experimental intensity measurements.     

Neutron scattering from intinerant ferromagnets just above Tc

Neutron scattering from itinerant ferromagnets at and just above T_c is studied on the basis of a simple band model with no short range order. Results are found for scattering line widths for small momentum and energy transfers which are substantially independent of band parameters. Some comparison with experiment is attempted.