Ab initio configuration interaction study on the electronic structure of the X2Σ+, B2Σ+ and 32Σ+ states of SiO+

The energy levels and electronic structure of the X²Σ⁺, B²Σ⁺ and 3²Σ⁺ states of SiO⁺ are studied using ab initio configuration interaction (CI) calculations at and around their equilibrium internuclear distances R _e. Spectroscopic constants and the vertical excitation energy from the SiO⁺ X²Σ⁺ state are predicted for the 3²Σ⁺ state. Based on the calculated CI wavefunctions, avoided crossings of the potential energy curve for the 3²Σ⁺ state and a near-degeneracy effect in the avoided crossing region are examined. The effects of the mixing of excited configuration state functions in the total electronic wavefunctions for the 1–3 ²Σ⁺ states are investigated by analysing correlation energies in terms of the contributions from classes of excited configurations. The importance of both the near-degeneracy effect and the correlation energy effect in describing correctly the electronic structure of the 3 ²Σ⁺ state in the neighbourhood of its R _e is discussed.     

High-resolution infrared Fourier transform spectroscopy of SO in the X3Σ− and a1Δ electronic states

The v = 1 ← 0 vibration-rotation absorption bands of ³²S¹⁶O, ³⁴S¹⁶O, and ³²S¹⁸O in the ground electronic state, X³Σ⁻, and the v = 1 ← 0 vibration-rotation band of ³²S¹⁶O in the first excited electronic state, a¹Δ, were measured at 0.004 cm⁻¹ unapodized resolution with a high-resolution Fourier transform spectrometer coupled to a long path absorption cell. The v = 2 ← 0 vibration-rotation band of ³²S¹⁶O in the X³Σ⁻ state was also observed. Line positions for P- and R-branch transitions up to N = 44 for ³²S¹⁶O have been measured and analyzed yielding improved molecular parameters. The present measurements are compared with previous infrared and microwave measurements.     

Ab initio calculations of electronic structure of anatase TiO2

This paper presents the results of the self-consistent calculations on the electronic structure of anatase phase of TiO2. The calculations were performed using the full potential-linearized augmented plane wave method (FP-LAPW)in the framework of the density functional theory (DFT) with the generalized gradient approximation (GGA). The fullyoptimized structure, obtained by minimizing the total energy and atomic forces, is in good agreement with experiment.We also calculated the band structure and the density of states. In particular, the calculated band structure prefers an indirect transition between valence and conduction bands of anatase TiO2, which may be helpful for clarifying theambiguity in other theoretical works.     

Ab initio electronic band structure study of III–VI layered semiconductors

We present a total energy study of the electronic properties of the rhombohedral γ-InSe, hexagonal ε-GaSe, and monoclinic GaTe layered compounds. The calculations have been done using the full potential linear augmented plane wave method, including spin-orbit interaction. The calculated valence bands of the three compounds compare well with angle resolved photoemission measurements and a discussion of the small discrepancies found has been given. The present calculations are also compared with recent and previous band structure calculations available in the literature for the three compounds. Finally, in order to improve the calculated band gap value we have used the recently proposed modified Becke-Johnson correction for the exchange-correlation potential.     

Ab initio study of PN electronic states – a qualitative interpretation of the perturbation and predissociation effects on observed transitions

Valence and high electronic states of PN have been calculated with accurate quantum chemistry methods. The variety of theoretical methods used includes complete active space self-consistent field, multireference configuration interaction and the newly developed explicitly correlated coupled cluster methods. The large correlation-consistent atomic orbitals basis sets AVQZ, AV5Z and AV(5+d)Z are used for the potential energy curves calculations in the bonding and long-range regions. The spectroscopic constants (R_e, B_e, ω_e, ω_ex_e, α_e, D_e, T_e) and the vibrational levels of the bound valence states (X¹Σ⁺, A¹Π, a³Σ⁺, d ³Δ, e³Σ^?, C¹Σ^?, b³Π, D ¹Δ and E¹Σ⁺ and some higher bound states) are determined and compared with experimental findings when available. Significant spin–orbit interactions between triplet states and A¹Π and E¹Σ⁺ excited states are found near the crossing points of the potential energy curves and could explain predissociation phenomena and the perturbations of the vibrational levels experimentally observed for PN in their A¹Π and E¹Σ⁺ states.     

Ab initio study of surface electronic structure of phosphorus donor impurity on Ge(111)-(2×1) surface

We present the results of numerical modeling of the electronic properties of the Ge(111)-(2 × 1) surface in the vicinity of a P donor impurity atom near the surface. We have shown that, in spite of well-established bulk donor impurity energy level position at the very bottom of the conduction band, the surface donor impurity might produce an energy level below the Fermi energy, depending on impurity atom local environment. It has been demonstrated that the impurity located in subsurface atomic layers is visible in scanning tunneling microscopy experiment. The quasi-one-dimensional character of the impurity image observed in scanning tunneling microscopy experiments is confirmed by our computer simulations.     

Ab initio potential surfaces for the à and states of HCN+

Ab initio configuration interaction calculations for the à ²Σ⁺ and states of HCN⁺ are presented. Minima occur at r _CH = 2·03 a ₀, r _CN = 2·25 a ₀ (à ²Σ⁺) and r _CH = 2·75 a₀, r _CN = 2·26 a ₀ (). The potential surface for the state has a local maximum as the hydrogen atom is pulled away from CN. The barrier height is calculated to be 0·27 eV.     

Rotational structure of the origin band in the 1A′ ←X1σ+ electronic transition of C4H− and C4D−

The rotational structure of the origin band for the ¹A′←X¹σt⁺ electronic transition, lying just below the electron affinity of C⁴H, was recorded by means of a two-colour resonant photodetachment technique. This allowed a determination of the rotational constants in the X¹σt⁺ ground and ¹A′ dipole bound excited state. The low lying A²II excited state of C⁴H is inferred to be the parent of the dipole bound state. The excited electronic state is deduced to have a nonlinear planar structure whereas the ground is linear according to the spectral analysis. The rotational constants have been obtained: B′; = 0.1552(2)cm^?1 for the X¹σt⁺ state, and A′ = 30.73(1), B′ = 0.1587(2), C′ = 0.1581(2)cm^?1 for the ¹A′ state.     

Ab initio study of the (2 × 2) phase of barium on graphene

We present a first-principles density functional theory study on the structural, electronic and dynamical properties of a novel barium doped graphene phase. Low energy electron diffraction of barium doped graphene presents clear evidence of (2 × 2) spots induced by barium adatoms with BaC₈ stoichiometry. First principles calculations reveals that the phase is thermodynamically stable but unstable to segregation towards the competitive BaC₆ monolayer phase. The calculation of phonon spectrum confirms the dynamical stability of the BaC₈ phase indicating its metastability, probably stabilized by doping and strain conditions due to the substrate. Barium induces a relevant doping of the graphene π states and new barium-derived hole Fermi surface at the M-point of the (2 × 2) Brillouin zone. In view of possible superconducting phase induced by foreign dopants in graphene, we studied the electron–phonon coupling of this novel (2 × 2) obtaining λ = 0.26, which excludes the stabilization of a superconducting phase.     

Vibrational Analysis of the A3Π0−X1Σ+ and B3Π1−X1Σ+ Subsystems of the GaBr Molecule

Abstract

The emission band spectrum of gallium monobromide has been excited in a dc hollow cathode discharge. bands of the ³Π_0,1?X¹Σ⁺ system, lying in the range from 340 to 370 nm have been recorded at high resolution and measured. The previous vibrational analysis has been revised and corrected. New vibrational assignment has been proposed and improved vibrational constants of the upper and lower electronic states have been determined.     

Ab initio electronic structure of the Ge(111)-(2 × 1) surface in the presence of surface vacancy. Application to STM data analysis

We present the results of ab initio modeling of Ge(111)-(2 × 1) surface in the presence of atomic vacancy in surface bilayer. We showed that simple crystal structure defect affects surface electronic structure to the extent comparable with the influence of doping atom. We demonstrated the strong difference of surface LDOS structure above surface defects of different kind. We have proved that spatial oscillations of LDOS exist around individual surface vacancy in the same tunneling bias range as in case of donor doping atom on Ge(111)-(2 × 1) surface.     

Theoretical study of the Renner-Teller A 2A1 − X 2B1 system of NH2

(Molec. Phys., 1994, 81, 1445–1461)     

An ab initio study of the hyperfine structure in the X2 Π electronic state of HCCS–calculation of vibronically averaged components of the anizotropic hyperfine tensor

The results of ab initio calculations of the vibronically averaged components of the anisotropic magnetic hyperfine tensor in the low-lying vibronic species of the X²Π electronic state of the HCCS radical are reported. The electronically averaged hyperfine coupling constants for hydrogen, deuterium, ¹³C and ³³S are obtained as functions of two bending vibrational modes by the density functional theory method. The vibronic wave functions are calculated with the help of a variational approach which takes into account the Renner–Teller effect and spin-orbit coupling. The results of ab initio calculations are compared to the corresponding experimental findings.     

Theory of the electronic structure of Ga1-yInyNxAs1−x and related alloys

Abstract

We present a quantitative k.P Hamiltonian which describes analytically the composition dependence of the energy gap, interband momentum matrix element, band edge effective masses and conduction band dispersion of GaN_XAs_1?x alloys for low N concentrations (x < ～ 0.05). The model has been confirmed using an sp³s? tight-binding Hamiltonian whose results agree well both with experiment and with previous pseudopotential calculations. The model should be of wide use to guide the future development of this material system and its applications.     

The vibrational structure of bromocyanoacetylene cation in the X̃2π and Ã2π electronic states studied by emission and laser exci

The vibrational frequencies of bromocyanoacetylene cation in its ground and first excited electronic states have been obtained by recording and analysing the emission and laser excitation spectra of the òπ-X̃²π transition. In the emission experiments the ions are produced rotationally cooled to ca. 10 K by means of a supersonic free jet and in the laser excitation measurements to ca. 100 K by Penning ionisation followed by collisional relaxation. The resulting narrowing of the vibronic bands in the spectra is such that the vibrational frequencies of most of the fundamentals could be inferred to within ± 2 cm⁻¹.