Flip motion of heterogeneous buckled dimers on Ge(0 0 1) by electron injection from STM tip

Surface motion of a topological defect between p(2×2) and c(4×2) structures, a “kink”, across buckled Sn-Ge and Si-Ge dimers on Ge(0 0 1) surfaces was investigated using scanning tunneling microscopy. Energy thresholds of π^∗ electrons for flipping these dimers in the kink are obtained by analyzing the kink surface motion. Electronic states of these systems and energy barriers for flipping the dimers are examined by first-principles calculations for considering elementary processes of the electronically-excited flip motion of the dimers. We propose that the flip motion is caused by a resonant scattering of the π^∗ electrons with localized electronic states at the kink.     

High-Resolution Survey of the Visible Spectrum of NiF by Fourier Transform Spectroscopy

High-resolution spectra of NiF have been recorded in emission by Fourier transform spectroscopy using a very stable discharge source. The 0-0 bands of 14 electronic transitions have been studied, 6 of them for the first time. This work confirms the presence of 5 low-lying spin components X²Π_3/2, [0.25]²Σ⁺, [0.83]A²Δ_5/2, [1.5]B²Σ⁺, and [2.2]A²Δ_3/2 as known from previous laser-induced fluorescence experiments. Eight electronic states are now identified in the 18 000-24 000 cm⁻¹ range above the ground X²Π_3/2 state. Electronic assignments for these excited states are not always obvious because of violations of the selection rules and unusual fine structure parameters. We think that some of the upper states are spin components of quartet states. In such a congested spectrum, high-resolution spectra are best analyzed in conjunction with an energy level diagram constructed mainly by dispersed low resolution laser-induced fluorescence.     

Type I FA (Rb, Cs) and II FA (Li, Na) tunable laser activities and donor-acceptor properties of O and O at KCl (001) surface: first principle calculations

Type I F_A (Rb⁺, Cs⁺) and II F_A (Li⁺, Na⁺) tunable laser activities, adsorptivity and donor-acceptor properties of O and O⁻ adsorbates at the flat surface of KCl crystal were investigated using an embedded cluster model and ab initio methods of molecular electronic structure calculations. Ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field of the host surface, and the nearest neighbor ions to the defect site were allowed to relax to equilibrium. Based on the calculated Stokes shifted optical transition bands, F_A tunable laser activities were found to be inversely proportional to the size of the dopant cation (Li⁺, Na⁺, Rb⁺, Cs⁺) relative to the host cation (K⁺). This relation was explained in terms of the axial perturbation of the impurity cation. The probability of orientational bleaching attributed to the RES saddle point ion configuration along the 〈110〉 axis was found to be inversely proportional to the size of the dopant cation, with activation energy barriers of ca. 0.44-3.34 eV. Surface relaxation energies of type II F_A centers were more important than those of type I F_A centers. In terms of defect formation energies, the products of type II F_A center imperfection were more stable than those of type I F_A. The difference between F or F_A band energies and exciton bands depended almost exclusively on the size of the positive ion species. As far as the adsorptivity of O and O⁻ is concerned, the results confirm that surface imperfection enhances the adsorption energies by ca. 4.38-16.37 eV. O and O⁻ penetrate through the defect-containing surface. The energy gap between the adsorbate and the defect containing surface and the donor-acceptor property of adsorbate play the dominant role in the course of adsorbate substrate interactions and the results were explained in terms of electrostatic potential curves and Mulliken population analysis.     

Photoionization cross sections of Fe XXI

Total and partial photoionization cross sections for (Fe XXI+hν→Fe XXII+e) are presented for the ground and excited bound states with n?10 and l?9. Fe XXI is prevalent in high-temperature astrophysical plasmas as well as in photoionized plasmas excited by hard X-rays. Results are reported for the first time for the high-energy photoionization with core excitations to n=2,3 states. Details of photoionization, especially the high-energy features that often dominate considerably over the low energy ones, are illustrated. These prominent features will affect the photoionization and the recombination rates in high-temperature plasmas. Calculations are carried out in the close coupling (CC) approximation using the R-matrix method. A large CC wavefunction expansion for Fe XXII which includes the ground and 28 excited core states from n=2 and 3 complexes and spans over a wide energy range is used. A total of 835 discrete bound states of Fe XXI in the singlet, triplet, and quintet symmetries are obtained. Total photoionization cross sections, σ_PI(nLS), for ionization into all 29 states are presented for all 835 final bound states and partial photoionization cross sections, σ_PI(g,nLS), for ionization into the ground ²P⁰ state of the core are presented for 685 states. While the n=2 core excitations are at relatively lower energy range (within 15 Ry from the ionization threshold), the n=3 excitations lie at considerably higher energy, 73 Ry and above, yet introduce resonant features and enhancements more prominent than those of n=2 states. Larger numbers of resonances are formed due to Rydberg series of autoionizing states converging on to the 29 core states. However, most noticeable structures are formed in the excited state cross sections by the photoexcitation-of-core (PEC) resonances in the photon energy range of 73-82 Ry. All these high-energy features are absent in the currently available results. The present results should enable more accurate modeling of the emission spectrum of highly excited plasma from the optical to far-ultraviolet region.     

Theoretical investigation of the molecular structure and transition dipole moments of the NaK low lying electronic states

The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK⁺ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of ²Σ⁺, ²Π, and ²Δ symmetries has been calculated up to their dissociation limit Na(4d) + K⁺ and Na⁺ + K(6s). Their spectroscopic constants (R_e, D_e, T_e, ω_e, ω_eχ_e, and B_e) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of ²Σ⁺, ²Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na⁺K and NaK⁺. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.     

Effects on spectroscopic properties for several low-lying electronic states of CS molecule by core-valence correlation and relativistic corrections

The potential energy curves (PECs) of six low-lying electronic states (X¹Σ⁺, a³Π, a′³Σ⁺, d³Δ, e³Σ⁻ and A¹Π) of CS molecule have been investigated using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach with large correlation-consistent basis sets. Effects on the PECs by the core-valence correlation and relativistic corrections have been taken into account. And the two corrections are performed at the level of cc-pV5Z basis set. The way to consider the relativistic corrections is to use the second-order Douglas-Kroll Hamiltonian approximation. Using the CCSD(T), MRCI and MRCI with the Davidson modification (MRCI + Q), the PECs of electronic states involved are extrapolated to the complete basis set (CBS) limit. With the PECs, the spectroscopic parameters (T_e, R_e, ω_e, ω_ex_e, ω_ey_e, α_e, β_e, γ_e and B_e) of the six low-lying electronic states are determined. These parameters are in excellent agreement with the experimental data. The complete vibrational states are computed for the six low-lying electronic states when the rotational quantum number J equals zero, and the inertial rotation constants of the first 23 vibrational states are reported, which agree favorably with the RKR data. Comparison with the measurements shows that the two-point total-energy extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.     

Charge ordering in amorphous WOx films

We report on the observation of highly anisotropic viscous electronic conducting phase in amorphous WO_1.55 films that occurs below a current (I)- and frequency (f  )-dependent temperature T^∗(I,f)$T^{\ast }(I,f)$. At T<T^∗(I,f)$T<T^{\ast }(I,f)$ the rotational symmetry of randomly disordered electronic background is broken leading to the appearance of mutually perpendicular metallic- and insulating-like states. A rich dynamic behavior of the electronic matter occurring at T<T^∗(I,f)$T<T^{\ast }(I,f)$ provides evidence for an interplay between pinning effects and electron–electron interactions. The results suggest a dynamic crystallization of the disordered electronic matter, viz. formation of sliding Wigner crystal, as well as the occurrence of quantum liquid-like crystal or stripe phase at low drives.     

Photoluminescence and transport in selectively doped p-GaAs/AlGaAs quantum wells: manifestation of the upper Hubbard band

By selective doping (Be) of the well and barrier regions of GaAs/Al_0.3Ga_0.7As structures we have realized the situation where the upper Hubbard band (A⁺ centers) has been occupied by holes in the equilibrium. We studied the temperature behavior of the Hall effect, variable range hopping (VRH) conductivity and the photoluminescence (PL) spectra of the corresponding structures. The experimental data demonstrated that the binding energy of the A⁺ states significantly increases with respect to 3D case and strongly depends on the well width (9 nm, 15 nm). The localization radii of the A⁺ states estimated from the transport data are of the order of the well widths.     

Measurement of the quadratic Zeeman shift of Rb hyperfine sublevels using stimulated Raman transitions

We demonstrate a technique for directly measuring the quadratic Zeeman shift using stimulated Raman transitions. The quadratic Zeeman shift has been measured yielding Δν=1296.8±3.3 Hz/G² for magnetically insensitive sublevels (5S_1/2,F=2,m_F=0→5S_1/2,F=3,m_F=0) of ⁸⁵Rb by compensating the magnetic field and cancelling the ac Stark shift. We also measured the cancellation ratio of the differential ac Stark shift due to the imbalanced Raman beams by using two pairs of Raman beams (σ⁺, σ⁺) and it is 1:3.67 when the one-photon detuning is 1.5 GHz in the experiment.     

Spectroscopic studies of atmospheric interest on NO and NO

In recent years, high-resolution photoelectron spectroscopy and ab initio calculations have considerably revised and enlarged the understanding of the electronic structure of the NO and NO⁺ molecules. The experimental potential energy curves for the different electronic states of atmospheric interest molecules like NO and NO⁺ are constructed by using the Rydberg-Klein-Rees method as modified by Vanderslice et al. The ground state dissociation energies are determined by curve fitting technique using the five parameter Hulburt-Hirschfelder (H-H) function. The estimated dissociation energies are 6.381 and 10.693 eV for NO and NO⁺, respectively. These values are in good agreement with the literature values. The r-centroids and Franck-Condon factors (FC Factors) for the band system of B²Π_r-X²Π of NO and a³Σ⁺-X¹Σ⁺, A¹Π-X¹Σ⁺ of NO⁺ molecules have been calculated employing an approximate analytical methods of Jarmain and Fraser, and Nicholls and Jarmain. The absence of the bands in these systems is explained.     

Valence states of the SiS molecule: Analysis of perturbations in the A1Π-X1Σ+ system

The results of a detailed rotational analysis of bands of the A¹Π-X¹Σ⁺ systems both of ²⁸SiS and of ³⁰SiS are given. Perturbations caused by interactions with two singlet states, D¹Δ and C¹Σ^?, and with two triplet states, e³Σ^? and d³Δ, are analyzed. The use of three different methods, based (i) on Franck-Condon factors, (ii) on isotope shifts, and (iii) on the identification of perturbing levels which cross more than one vibrational level of A¹Π, to determine the vibrational numbering in the perturbing states is examined and for three of the above electronic states an unambiguous numbering is derived. Two alternative consecutive vibrational numberings for D¹Δ are suggested. Method (i) is unreliable here, because of the very high vibrational quantum numbers of the levels that perturb A¹Π. RKR potentials are constructed and thence, with calculated Franck-Condon factors, values of the electronic interaction constants are derived for the interactions between the perturbing states and A¹Π. The values so obtained are compared with those for CO, CS, and SiO, and with estimates from ab initio calculations.     

Theoretical investigations of the SH and LiS cations

Reliable theoretical data on spectroscopy and spin-orbit matrix elements are computed for the lowest electronic states of SH⁺ and LiS⁺ ions. Accurate spectroscopic predictions for their excited electronic states are given. For SH⁺, polarization minima at large internuclear distances are located in addition to the strongly bound electronic states already known. For LiS⁺, our calculations confirm that the electronic ground state of this ion is of ³Σ⁻ species and reveal the existence of a ¹Δ state presenting a potential well as deep as the potential of the ground state. Moreover, the LiS⁺ electronic excited states potential energy curves possess shallow potential minima in the molecular region and at long-internuclear distances. Generally, these shallow minima may be populated during low energy collisions between the corresponding atomic fragments. Finally, spin-orbit calculations have allowed giving accurate determinations of the spin-orbit splittings for these cations and elucidation of the predissociation mechanisms of SH⁺ leading to the formation of the S⁺ and H species in their electronic ground states. Accordingly, long-lived SH⁺ ions can be found in the X³Σ⁻, a¹Δ and b¹Σ⁺ electronic states and the rovibrational levels of LiS⁺ in its electronically excited and ground states should be weakly perturbed.     

Vortex structure of Gross-Pitaevskii model

The vortex line of the Gross-Pitaevskii model is studied. The kinetic helicity of the vortex is discussed, and vortex structure is classified by the Hopf index, linking number in geometry. A mechanism of generation and annihilation of vortex lines is given by the method of phase singularity theory. The dynamic behavior of the vortex at the critical points is discussed in detail, and three kinds of length approximation relations at the neighborhood of a critical point are given: l ∝ (t − t^∗)^1/2, l ∝ t − t^∗, l = const.     

Ion formation in laser-irradiated cesium vapor

We study theoretically the formation of Cs⁺ and during cw laser radiation resonant with 6s-7p transition of Cs atomic vapor. This is done by numerically solving rate equations for the evolution of atomic state and electron populations. The results of calculations for the atomic and molecular ions density at different values of laser power clarified that the associative ionization and Penning ionization process play an important role for producing the and Cs⁺, respectively, during the plasma formation. Also, the results showed that laser power of the order of 150 mW and 40-50 ns irradiation time are optimal in producing a fully ionized plasma.     

Inversion analysis of K 2 coupled electronic states with the Fourier grid method

We present a new determination of the potential curves and interactions of the coupled electronic states A ¹ Σ ⁺ _u and b ³ Π _u of the potassium dimer, based on new laser spectroscopy measurements within a molecular beam, combined with data available in the literature. We used a new global deperturbation approach, involving the Fourier Grid Hamiltonian method for energy level calculation. A standard deviation of 1.2 is obtained corresponding to a variance of 7.5×10 ^-3 cm^-1, representing a significant improvement compared to the standard deviation of 4 yielded by the traditional local deperturbation approach. Received 12 June 2001 and Received in final form 3 September 2001     

Studies on the Vibrational and Rovibrational Energies and Vibrational Force Constants of Diatomic Molecular States Using Algebraic and Variational Methods

Alternative expressions for vibrational and rotational spectrum constants and energies of diatomic molecular electronic states based on perturbation theory are suggested. An algebraic method (AM) is proposed to generate a converged full vibrational spectrum from limited energy data, and a potential variational method (PVM) is suggested to produce the vibrational force constants f_n and rotational spectrum constants using the perturbation formulae and the AM vibrational constants. The AM and PVM have been applied to study 10 diatomic electronic states: the X¹Σ_g⁺ and C¹Π_u⁻ states of H₂; the X¹Σ_g⁺, A³Σ_u⁺, B′³Σ_u⁻, and B³Π_g states of N₂; the X³Σ_g⁻, A³Σ_u⁺, and c¹Σ_u⁻ states of O₂; and the X¹Σ_g⁺ state of Br₂. Calculations show that (1) the AM E_υmax converges to the correct molecular dissociation energy; (2) the AM not only reproduce the input energies, but also generate the E_υ's of high vibrational excited states which may be difficult to obtain experimentally or theoretically; (3) the PVM vibrational force constants f_n may be used to measure the relative chemical bondstrengths of different diatomic electronic states for a molecule quantitatively.     

Relationships between lattice energy and electronic polarizability of AB crystals

The correlations between the electronic polarizability, determined from Clausius-Mosotti equation based on dielectric constant ε, and the lattice energy density u have been established for A^NB^8-N crystals, such as the systems of rock salt crystals (group I-VII, II-VI) and tetrahedral coordinated crystals (group II-VI, III-V). For the A^NB^8-N crystals systems, our present conclusions suggest that lattice energy density u decreases exponentially with increasing electronic polarizability, and the normal mathematical expression between lattice energy density u and electronic polarizability is u = pα^q, p and q depend on the type of crystals. For the same cation binary A^NB^8-N crystals systems, curve fitting equations have been obtained, and the relevant squares of the correlation coefficient R² are larger than 0.99, which show all lattice energy density u are in good exponential relation with electronic polarizability. These empirical equations will give more information on calculating lattice energy or electronic polarizability. New data of lattice energy have been calculated on the above equation u = pα^q, and a good linear trend in the calculating values along with the Zhang’s values has been obtained.     

Cross-section and rate coefficient calculation for electron impact excitation, ionisation and dissociation of H2 and OH molecules

The weighted total cross-section (WTCS) theory is used to calculate electron impact excitation, ionisation and dissociation cross-sections and rate coefficients of OH, H₂, OH⁺, H₂ ⁺, OH^- and H₂ ^- diatomic molecules in the temperature range 1500–15000 K. Calculations are performed for H₂(X, B, C), OH(X, A, B), H₂ ⁺(X), OH⁺(X, a, A, b, c), H₂ ^-(X) and OH^-(X) electronic states for which Dunham coefficients are available. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. One and two temperature (θ_e and θ_g respectively for electron and heavy particles kinetic temperatures) results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) = a (θ^b)exp (-c/θ).     

Ab initio calculation of neutral and singly charged Mgn (n?11) clusters

Under generalized gradient approximation (GGA), geometrical structure, size dependence of stability and electronic properties of neutral Mg_n, singly charged cationic Mg_n⁺ and singly charged anionic Mg_n⁻ clusters consisting of up to 11 atoms have been studied systematically by ab initio method within the norm-conserving pseudopotentials. In addition to the electronic shell effects, the “closed” geometrical structure can also enhance the stability of the clusters. The enhanced stability for the cationic cluster resulted from the removal of an antibonding electron is larger than that for the anionic cluster by promoting an extra electron to occupy a bonding orbital. The density of states (DOS) shows the increase in interaction between valence and unoccupied states leads to an increase in s-p hybridization.     

Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Pure rotational spectra have been measured for the ground electronic states of SbF and SbCl. The molecules were prepared by laser ablation of Sb metal in the presence of SF₆ or Cl₂, respectively. Their spectra were measured with a cavity pulsed jet Fourier transform microwave spectrometer. Although both molecules have two unpaired electrons, they are subject to Hund’s coupling case (c), and have X₁0⁺ ground states. The spectra have been interpreted with the formalism of ¹Σ⁺ molecules. For both molecules spectra of several isotopomers have been measured in the ground and first excited vibrational states. Large hyperfine splittings attributable to both nuclear quadrupole coupling and nuclear spin-rotation coupling have been observed. A Dunham-type analysis has produced unusually large Born-Oppenheimer breakdown parameters, which are interpreted in terms of the electronic structures of the molecules.