On the separation of initial and final state effects in photoelectron spectroscopy using an extension of the auger-parameter concept

First, we show that the quantity Δβ(i) = ΔE_A(kii) + 2ΔE_B(i) — ΔE_B(k) is directly related to the final state relaxation contribution ΔE_R(i) of the binding energy shift ΔE_B(i). ΔE_A(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell¹. It is shown that ΔR(P_2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations.     

The long-time behaviour of the electric-field autocorrelation function in a finite photon gas

We investigate an autocorrelation function of a soluble three-dimensional system, namely the temporal coherence functionC _E(t)∝<E(0)E(t)> of the thermal radiation field in a cube-shaped cavity for the stochastic electrical fieldE. In the thermodynamic limit,C _E(t) relaxes exponentially at intermediate times, but a “long-tail” behaviourC ₀(t)=At^?4 withA<0 is predominant for long times. In the case of a finite, but not too small, cavity lengthL obeyingΛ=hc/k _BT?L and at timest withct?L, C _E(t) is described by an asymptotic expansion in powers ofL ^?1 using generalized Riemann zeta functions. Surface-and shape-effects enhance the long-tail. In the case of very small cavities withL«Λ, we calculate an expansion ofC _E(t) in terms of exp(?L ^?1) and cosines. An oscillatory, but not strictly periodic, long-time behaviour is observed in this case.     

Investigation of crystal structure and new ellipsometric properties of hexagonal CdS epilayers

High quality hexagonal CdS epilayer was grown on GaAs (1 1 1) substrates by the hot-wall epitaxy method. The crystal structure of the grown CdS epilayers was confirmed to be the hexagonal structure by X-ray diffraction pattern and scanning electron microscopy image. The optical properties of the hexagonal CdS epilayers were investigated in a wide photon energy range between 2.0 and 8.5 eV using spectroscopic ellipsometry (SE) at room temperature. The data obtained by SE were analyzed to find the critical points of the pseudodielectric function spectra, 〈?(E)〉 = 〈?₁(E)〉 + i〈?₂(E)〉, such as E₀, E_1A, E_1B, E^0′, F₁, and two E₂ structures. In addition, the second derivative spectra, d²?(E)/dE², of the pseudodielectric function of hexagonal CdS epilayers were numerically calculated to determine the critical structures. Four structures, such as E^0′F₁, and two E₂ structures, from 6.0 eV to 8.0 eV were observed, for the first time, at 300 K by ellipsometric measurements for the hexagonal CdS epilayers.     

The microwave spectrum of IF5 in excited vibrational states: Accidental degeneracy and avoided crossing of the kl = 3 and kl = −1 levels in the state v9(E) = 1

Measurements of the microwave spectrum of the C_4v molecule IF₅ in the excited vibrational states v₉(E) = 1 and v₅(B₁) = 1 are reported for the transitions J12 ← 11 and J13 ← 12 (65–72 GHz). The considerable spectral perturbations produced by an accidental degeneracy and avoided crossing of the ψ^? (kl = 3) and ψ^? (kl = ?1) levels of the v₉(E) = 1 state have been measured and analyzed. A spectroscopic determination of the axial rotation constant C₉ is reported and its implications for the molecular structure of IF₅ discussed.     

Investigation of energy band gap and optical properties of cubic CdS epilayers

High quality cubic CdS epilayers were grown on GaAs (1 0 0) substrates by the hot-wall epitaxy method. The crystal structure of the grown epilayers was confirmed to be the cubic structure by X-ray diffraction patterns. The optical properties of the epilayers were investigated in a wide photon energy range between 2.0 and 8.5 eV using spectroscopic ellipsometry (SE) and were studied in the transmittance spectra at a wavelength range of 400-700 nm at room temperature. The data obtained by SE were analyzed to find the critical points of the pseudodielectric function spectra, 〈?(E)〉 = 〈?₁(E)〉 + i〈?₂(E)〉, such as E₀, E₁, E₂, E^′₀, and E^′₁ structures. In addition, the optical properties related to the pseudodielectric function of CdS, such as the absorption coefficient α(E), were investigated. All the critical point structures were observed, for the first time, at 300 K by ellipsometric measurements for the cubic CdS epilayers. Also, the energy band gap was determined by the transmittance spectra of the free-standing film, and the results were compared with the E₀ structure obtained by SE measurement.     

[2.2.2]Paracyclophane as a receptor for the cesium cation in the gas phase

By using electrospray ionisation mass spectrometry, it was proven experimentally that the cesium cation (Cs⁺) forms with [2.2.2]paracyclophane (C₂₄H₂₄) the cationic complex [Cs(C₂₄H₂₄)]⁺. Further, applying quantum chemical calculations, the most probable structure of the [Cs(C₂₄H₂₄)]⁺ complex was derived. In the resulting complex with a symmetry very close to C₃, the ‘central’ cation Cs⁺, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E(int), of the considered cation–π complex [Cs(C₂₄H₂₄)]⁺ was found to be ?73.2 kJ/mol, confirming the formation of this fascinating complex species as well. This means that [2.2.2]paracyclophane can be considered as a receptor for the Cs⁺ cation in the gas phase.     

Effect of kink-rounding barriers on step edge fluctuations

The effect that an additional energy barrier E_kr for step adatoms moving around kinks has on equilibrium step edge fluctuations is explored using scaling arguments and kinetic Monte Carlo simulations. When mass transport is through step edge diffusion, the time correlation function of the step fluctuations behaves as C(t)=A(T)t^1/4. At low temperatures the prefactor A(T) shows Arrhenius behavior with an activation energy (E_det+3?)/4 if E_kr<? and (E_det+E_kr+2?)/4 if E_kr>?, where ? is the kink energy and E_det is the barrier for detachment of a step adatom from a kink. We point out that the assumption of an Einstein relation for step edge diffusion has lead to an incorrect interpretation of step fluctuation experiments, and explain why such a relation does not hold. The theory is applied to experimental results on Pt(1 1 1) and Cu(1 0 0).     

An ESCA investigation of some thiocyanato complexes

A series of simple thiocyanato complex ions have been investigated as their tetraphenylphosphonium and potassium salts. The binding energies of N, C and S were determined as well as those of the metals. From the first-mentioned data effective charge-values were estimated for the atoms of the ligands. For this purpose linear relations E_b = kq + E_b0 were used that had been previously established within a scheme having C_1s (phenyl) as the internal standard.From the data thus obtained the effective charge on the metal atoms was estimated. For elements where we have sufficient data the same type of linear relation seems to he followed. Tentatively valid examples are E_b(Ni) = 6.74q_Ni + 848.3 eV and E_b(Pd) = 4.45q_Pd + 333.9 eV.In this interpretation the atoms of the metals are considered to be positively charged and surrounded by the negative charge of the electrons occupying the s band.It is further suggested for complexes with pronounced π backbonding (Pt(SCN)₄^2?, Pd(SCN)₄^2? and Hg(SCN)₄^2?) that the C 1s binding energy measured for the carbon atom of the SCN^? ligand is composed of the ionisation energy from the 1s level and an additional term corresponding to the intraligand π → π* transition.     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

The effect of pressure on impact ionisation and the Gunn effect in InAs

The pressure dependence of the threshold field for avalanche breakdown (E_A) and the Gunn effect (E_T) in InAs has been measured to 50 kbar. E_T increases approximately proportional to the effective mass when the effects of impact ionisation are eliminated. A brief comparison is made with the effects of pressure on E_T in other III–V semiconductors.     

Intensities and half-widths at different temperatures for the 201III←000 band of CO2 at 4854 cm−1

Measurements made at temperatures of 197, 233, and 294°K of the absolute intensities and self-broadening coefficients for the vibration-rotation lines of the 201_III←000 band of the ¹²C¹⁶O₂ molecule, are reported. From these measurements, values have been derived for the vibration-rotation interaction factor (F_VR), the purely vibrational transition moment (|R(O)|), and the intensity (S_Band). The results are: E_VR(m) = 1+(2.2±0.7)×10^?3m+(5.6±1.6)×10^×5m², |R(0)| = (2.064±0.017)×10^?3 debye, S_Band = 21,329±69 cm^?1km^?1atm^?1_STP. The results for the self-broadening coefficients are presented in the text.     

Emission and laser-excitation spectra of rotationally cooled methylcyanodiacetylene cation (A˜2EāX˜2 E) and photoelectron—photon

The A?²EāX?² E band system of rotationally cooled methylcyanodiacetylene cation has been studied by emission and excitation spectroscopies. Spectra were obtained by electron-impact ionisation of a seeded helium supersonic free jet and by Penning ionisation followed by laser excitation. These data enable the vibrational frequencies of most of the A₁ fundamentals to be inferred for the X?²E (to within ±2 cm^?1) andX?²E (to within ±4 cm?1) states. The fluorescence quantum yields and lifetimes of the cation prepared in selected levels of theA?²E andB?²A₁, excited states have been determined by photoelectron—photon coincidence measurements and yield a quantitative insight into the radiationless-decay pathways.     

Total photonuclear absorption cross section for Pb and for heavy nuclei in the Δ-resonance region

The partial sum σ⁽²⁾(E_γ) = Σ_i?2 σ(γ, in…), representing the inclusive cross section for all reaction channels in which at least two neutrons are emitted, has been measured with a quasimonochromatic photon beam obtained by the in-flight annihilation of monoenergetic positrons, and neutron multiplicity counting. These experimental results, taken with photon energies E_γ from 145 up to 440 MeV for Pb and with photon energies E_γ= 235 MeV and 330 MeV for Al, Cu, Zr, Sn, Ho, Ta and U, are subsequently used to determine the total photonuclear absorption cross section σ(tot: E_γ) and to study the dependence upon the mass number A of the normalized cross section σ(tot: E_γ)/A. These results are then compared with other information on the total photonuclear absorption cross section.     

The15N(p,α 0)12C reaction at stellar energies

The¹⁵N(ρ, α₀)¹²C reaction has been investigated in the energy range ofE _p (lab)=78-810keV. The measurement of the excitation functions and α-particle angular distributions involved solid targets as well as a quasi-point supersonic jet gas target. The determination of absolute cross sections has been carried out with the gas target. The observed energy dependence of the total cross sections can be described in terms of two-level Breit-Wigner shapes including the resonances atE _p (J ^π)=335(1^?) and 1,028(1^?)keV. The data lead to a zero-energy intercept of the astrophysicalS(E) factor ofS(0)= 65±4MeV-b. The angular distributions are asymmetric around 90° and require an additional amplitude in the reaction mechanism, which interferes predominantly with the 335 keV resonance. The origin of this background amplitude is discussed.     

Fascinating interaction of the ammonium cation with [2.2.2]paracyclophane: experimental and theoretical study

By means of electrospray ionisation mass spectrometry, it was evidenced experimentally that the ammonium cation (NH₄⁺) reacts with the electroneutral [2.2.2]paracyclophane ligand (C₂₄H₂₄) to form the cationic complex [NH₄(C₂₄H₂₄)]⁺. Moreover, applying quantum chemical calculations, the most probable conformation of the proven [NH₄(C₂₄H₂₄)]⁺ complex was solved. In the complex [NH₄(C₂₄H₂₄)]⁺ having a symmetry very close to C₃, the ‘central’ cation NH₄⁺ is coordinated by three strong bifurcated intramolecular hydrogen bonds to the corresponding six carbon atoms from the three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E(int), of the considered complex [NH₄(C₂₄H₂₄)]⁺ was evaluated as ?625.8 kJ/mol, confirming the formation of this fascinating complex species as well. It means that the [2.2.2]paracyclophane ligand can be considered as an effective receptor for the ammonium cation in the gas phase.     

Experimental study of the reactions of Si+(2P) ions with several small organic molecules at near thermal energies

The kinetics of the reactions of ground state silicon ions Si⁺(²P) with C₂H₆, CH₃OH, and CH₃CH₂OH has been investigated using a Selected Ion Flow Drift Tube technique (SIFDT). The reaction rate coefficients and the product distributions have been determined as functions of the reactant ion/reactant neutral average centre-of-mass kinetic energy (E _CM). The reactions studied are fast at thermal and near thermal energies and the reaction rate coefficients decrease by nearly one order of magnitude withE _CM increasing up to a few eV. It is shown that the energy dependences of the measured reaction rate coefficients can be described by the function of the formk ≈ 1/[1+ (E _CM/E _CM1) ^m ], whereE _CM1 andm are parameters which can be determined from the experimental data. The results are interpreted in terms of a simple model assuming the reactions to proceed via the formation of long-lived complexes. These intermediate complexes decompose with unimolecular rate coefficientsk _?1 andk ₂ back to the reactants and forward to the products, respectively. The ratiosk _?1/k ₂ can be approximated for reactions studied by a power law functionk _?1/k ₂ ∞ (E _CM) ^m .     

A boundary-value problem for dielectric spherical void in a homogeneous insulator by considering surface conductivity

In this paper, the boundary-value problem satisfying the Dirichlet condition has been solved for the case of a dielectric, spherical void inside a homogeneous insulator by considering surface conductivity. Mathematical equations have been derived to calculate the respective electric fields E_i(t)and E_e(t) inside and outside spherical gas voids that exist within an insulator by considering the surface conductivity γ_s of gas voids having an electric permittivity of ε_i and conductivity γ_i under DC (ωτ⪡1) and AC (ωτ⪢1) conditions. The expression for the dipole moment of a polarized spherical dielectric particle has been obtained in accordance with the determined electric field E_i(t). The derived expressions are then applied to calculate reciprocal interaction force between the spherical particle and metallic electrodes, which is very considerable for the dielectric separation processes in the DC and AC cases.     

Testing QCD: Direct photons ine + e − collisions

We discuss QCD predictions for the production of direct photons ine ⁺ e ^? collisions,e ⁺ e ^?→ γ^*→γ+ hadrons (C=+). A simple derivation of the QCD results for the structure functions is presented. These turn out to be exactly predicted by the theory, in contrast to hadron production where only the change withQ ² is predictable. We also take up the phenomenology of this process. A dramatic rise of the γ/π⁰ ratio withz=E _γ/E _B (E _π/E _B ) and withQ ² is predicted.