Observation of Interference Effects in (e, 2e) Electron Momentum Spectroscopy of SF6 (cited: 1)

Two-dimensional electron density map (2D map) of binding energy and relative azimuthal angle (i.e., momentum) for the outer-valence molecular orbitals of SF₆ has been measured by a highly sensitive electron momentum spectrometer with noncoplanar symmetric geometry at the impact energy of 1.2 keV plus binding energy. The experimental electron momentum profiles for the relevant molecular orbitals have been extracted from the 2D map and interpreted on the basis of the quantitative calculations using the density functional theory with B3LYP hybrid functional. For the outermost F2p nonbonding orbitals of SF₆, the interference patterns are clearly observed in the ratios of the electron momentum profiles of molecular orbitals to that of atomic F2p orbital.     

Laser-assisted (e, 2e) collisions in helium

The influence of a strong laser field on the dynamics of fast (e, 2e) collisions in helium is analyzed in the asymmetric, coplanar geometry. The interaction of the laser field with the incident, scattered and ejected electrons is treated in a non-perturbative way, while the remaining interactions are treated by using first order perturbation theory. Detailed calculations are performed for an incident electron energyE _{k i}=600 eV, an ejected electron energyE _{k B}=5 eV and a scattering angle θ _A =4°. The influence of the laser parameters (photon energy, intensity and direction of polarization) on the angular distribution of the ejected electron is analyzed. We find that in general the triple differential cross sections are strongly dependent on the dressing of the projectile and the target by the laser field.     

Angular distributions of electrons in the (e, 3e) reaction

The differential cross sections for the Kr (e, 3e) Kr⁺⁺ reaction are calculated (by using correlated wave function) in the case of high incident energy (5 keV) for the three terms of the final Kr⁺⁺ (4p ⁴) ion. We have performed an ab initio calculation on the basis of the first Born approximation using correlated wave functions for the target. The agreement with the first available (e, 3e) experimental data is fairly good. Other typical experimental situations are proposed and discussed.     

An (e,2e) study of ammonia: Binding energies and momentum distributions of valence electrons

The valence shell electronic structure of NH₃ is studied in an (e,2e) experiment with symmetric non-coplanar geometry. The momentum distributions obtained for the separate orbitals are compared with those calculated from several approximate wavefunctions. The 3a₁ distribution is found to be particularly sensitive to the form of the wavefunction.     

Triple differential generalized oscillator strength of direct and resonance He(e, 2e)He+ reaction at high incident energies

The triple differential cross section and triple differential generalized oscillator strength of the direct and resonance He(e, 2e)He⁺ reaction in the first Born approximation for incident energiesE ₀≥4keV are calculated. For the direct (e, 2e) process our results obtained in definite structure models of the atom are found to be in good agreement with the available experimental data and theoretical estimates. The resonance profiles calculated in these models exhibit a complicated structure formation of overlapping¹ P and¹ D autoionization states (AIS) excited in the (e, 2e) reaction. The specific kine-matical conditions, when the overlap and interference of the¹ P and¹ D resonances are small and the¹ P and¹ D AIS yields can be measured separately, are discussed. It is also shown that in a certain range of ejection angles and at large momentum transfers (Q>2au) the yield of the¹ D AIS dominates over the¹ P resonance yield.     

Ground state correlations in H2 measured by the (e,2e) technique

The relative intensities for exciting the 1sσ_g, 2pσ_u, 2pπ_u, and 2sσ_g states of H₂ are measured in a 1200 eV noncoplanar symmetric (e,2e) experiment on H₂. Momentum distributions are obtained at separation energies corresponding to the various transitions. The ratio of transition probability to the excited states relative to the ground state is strongly dependent on the ion recoil momentum q, having a minimum value of approximately 2% at small q. The excited state cross sections are sensitive to electron correlation effects and the data are compared with calculated cross sections using a configuration interaction wavefunction for H₂.     

The Orthogonal (e,e,e)‐Tris‐Adduct of 9,10‐Dimethylanthracene with C60‐Fullerene: A Hidden Cornerstone of Fullerene Chemistry. Preliminary Communication

Tris(9′,10′‐dimethyl[9,10]ethanoanthracene[11′,12′: 1,9;11″,12″: 16,17;11′′′,12′′′: 30,31])[5,6]fullerene C₆₀, the orthogonal (e,e,e)‐tris‐adduct of C₆₀ and 9,10‐dimethylanthracene, was obtained from [4+2]‐cycloaddition (Diels–Alder reaction) at room temperature. The thermally unstable orange red (e,e,e)‐tris‐adduct was purified by chromatography and was isolated in the form of red monoclinic crystals. Its C₃‐symmetric addition pattern was established spectroscopically. Its structure could be further investigated by single crystal X‐ray diffraction. The (e,e,e)‐tris‐adduct of C₆₀ and 9,10‐dimethylanthracene has earlier been suggested as intermediate and reversibly formed critical component in ‘template directed’ addition reactions of C₆₀. This previously elusive compound has now been isolated and structurally characterized.     

The geometry of the propynol cation,HC3O+

The geometry of a potential interstellar molecule, the propynol cation, HC₃O⁺, is determined by split-valence plus polarization (6-31G*) SCF method with the inclusion of electron correlation effects by third order Møller—Plesset perturbation theory (MP3). The 6-31G* MP3 geometry is: r_e(CO) = 1.125, r_e(CC) = 1.351, r_e(CC) = 1.214, r_e(CH) = 1.078 A, and thus a B_e of 4.421 GHz.     

The geometry and vibrational frequencies of formyl cyanide,CHOCN

The structure of the recently prepared formyl cyanide molecule has been determined by ab initio calculations up to the level of split valence plus polarization with inclusion of electron correlation (6-31G¹MP3). The 6-31G¹MP3 geometry is: r_e(CN) = 1.160, r_e(C-C) = 1.476, r_e(CO) = 1.207, r_e(CH) = 1.098 Å, α_e(C-CN) = 178.32°, α_e(CCO) = 121.63°, and α_e(HCO) =     

Gas-phase conformations and exciton couplings in 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene

The conformations and exciton couplings in 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene (THDC) have been studied using resonance-enhanced two-photon ionization spectroscopy in a supersonic jet expansion. It has been estimated from the spectral analysis that 90% of THDC exists in the twist-boat (TB) conformation; the chair (C) conformer constitutes the remaining 10%. Most of the vibronic activity in the spectrum of THDC is associated with the symmetric flapping of the aromatic rings of the TB conformer. The observed S₁/S₂ exciton splitting of the TB conformer is 100 cm^?1. The S₁/S₂ transition of the C conformer is found to be forbidden. The exciton splittings of the C and TB conformers were estimated by the spectral analysis of two deuterated isotopomers of THDC. The estimated exciton splittings of the C and TB conformers are 14.7 and 101.9 cm^?1, respectively. The supramolecular model of bichromophores with identical chromophores at the CIS/6-31+G(d)//HF/6-31+G(d) level of theory predicted electronic coupling energies that are very close to the experimental exciton coupling energies.     

Ionisation dynamics at intermediate momentum transfer: an (e, 2e) investigation on argon

Relative triple differential cross section for the coplanar asymmetric (e, 2e) reaction in argon have been measured at 1.5 KeV incident energy and 40 eV ejected electron energy in several kinematics. Depending on the scattering angle, ? _a , the chosen kinematics select either ionising collisions belonging to the Bethe ridge (? _a =9.2°) or processes in the intermediate region between the pure dipolar and binary regimes. The more relevant finding is the presence of a minimum in the recoil lobe, almost opposite to the direction of the momentum transfer. This feature is qualitatively explained by a first Born model, which describes the ejected electron by a Coulomb wave-function. This result suggests that in the investigated kinematics the interaction of the slow ejected electron with the residual ion is the dominant effect beyond the first order electron-electron interactions.     

Hydrodynamic voltammetry at channel electrodes: Part II. Theory of first-order kinetic collection efficiencies

The theory of first-order kinetic collection efficiencies at the double channel electrode is developed for the following two schemes: (I) A±n₁e→B (at the generator electrode), B→^kP (in solution), B±n₂e→Y (at the detector electrode), (II) A±n₁e→B, B→^kA, B±n₂e→Y. The exact expressions for the kinetic collection efficiencies are obtained as ascending and asymptotic series with respect to the kinetic parameter. Further, approximate formulae in exponential forms are given, which hold within an error of about 2% for conventional electrode geometry. Finally, the validity of the approximate procedure, which has been used previously to obtain the kinetic collection efficiencies for fast homogeneous reactions, is discussed in comparison with the present theory.     

Comparison of the effects of symmetric versus asymmetric H bonding on 2H and 17O nuclear quadrupole coupling constants: Application to formic acid and the hydrogen diformate anion

In this paper, we analyse the effects on the nuclear quadrupole coupling behaviour of ²H and ¹⁷O nuclei of a shift in H-bond character from asymmetric to symmetric. Using ab initio methods, the coupling amplitudes (nuclear quadrupole coupling constant e²_qQ/h) coupling anisotropies (asymmetry parameter η), and orientations of the electric field gradient (EFG) principal axis (PA) system of the H-bonded deuterium and oxygen nuclei in the formic acid dimer and related monomers, and the deuterium diformate anion are calculated. In addition, the relative contributions to the ²H and ¹⁷O EFGs of nuclear and electronic terms, and also the convergence of the EFG as a function of contributions from increasingly distant nuclei in the molecule are investigated. The trends in the calculated ¹⁷O EFGs on going from an asymmetric to a symmetric H-bonded environment are correlated with experimental nqr data in order to establish the hitherto unknown e²qQ/h sign, EFG assignments and PA orientation of symmetrically H-bonded oxygen. The possibility that the e²qQ/h value of deuterium is negative for symmetric H bonds is discussed, and difficulties in the computation of ²H EFGs for symmetric - as distinct from asymmetric - H-bonded systems are pointed out. In strong disagreement with assumptions in the literature, it is found that nearest neighbour terms do not dominate the ²H EFG in symmetrically H-bonded systems.     

The yields of1 P and1 D resonances in the He(e, 2e)He+ reaction

In the first Born approximation the dependence of the yields of the¹ P and¹ D resonances in the He(e, 2e)He⁺ reaction on the momentum transfer in the recoil peak region at incident energiesE ₀=1000 eV is studied. It is shown that in a certain range of the ejection angle and for the large momentum transfer the yield of the¹ D resonance dominates over the¹ P resonance one.     

Effective atomic number and electron density of marble concrete

The effective atomic numbers (Z _eff) and effective electron density (N _e) of different type concrete have been measured and the results were compared with the calculation obtained using the mass attenuation coefficients (μ/ρ) obtained via XCOM in the photon energy range of 1 keV–100 GeV. Six different concrete in where marble has been used in the rate of 0, 5, 10, 15, 20, 25 %, has been used in the study.     

Distorted-wave Born approximation calculations of (e, 2e) reactions

The distorted-wave Born approximation (DW-BA) is discussed and samples of calculations are presented for ionization of the 2p inner shell of Ar, the 5p, 5s and 4d shells of Xe, and for ionization of He in asymmetric perpendicular plane geometry. Agreement with measurements of inner shell ionization of Ar is excellent. It is pointed out that triple differential cross sections for ionization of heavy atoms can exhibit much structure, which presents a challenge to both theory and experiment. Particular cases of 5s and 4d ionization of Xe are given as examples of situations worthy of experimental investigation. Comparison is made with very recent measurements of ionization of He in asymmetric perpendicular plane geometry. In agreement with experiment, DWBA shows at all incident energies a single main peak at φ=180°, where φ is the angle between the outgoing electrons. It is demonstrated that at high energies this peak arises from a double collison mechanism. This contrasts with energy-sharing ionization into the perpendicular plane where the double collision mechanism, dominant at high energies, gives a peak at φ=90°, and where with reducing energy this peak is replaced by one at φ=180° coming from the single collision mechanism. Suggestions are made for further experiments.     

Angular distributions in the double ionization of noble gases by electron impact

Electron-impact double ionization of noble gases is investigated theoretically for the case of high incident energies (5 keV). An ab initio calculation is made including partial correlation in the initial state as well as in the final state. The results of the calculations are compared with those of other theories and with the first available (e, 3e) experimental data on krypton 4p ⁶.     

Analysis of low energy X-ray and excitation spectra of Ba 35+

We present a theoretical analysis of the low energy X-ray spectra of the Ba³⁵⁺ + e ^- system, in the energy region below 2 keV, for comparison with future experiments. In a recent study carried out at the National Institute of Standards and Technology, scandium-like Ba³⁵⁺ ions were created, trapped and excited using an Electron Beam Ion Trap and an electron beam with kinetic energy of 2.35 keV. The theory agrees well with experiment for X-ray energies in the region 2–5 keV. The experiment also gives evidence suggestive of a large cross section for X-ray production in the region below 2.0 keV. We include the contribution to the X-ray spectra of collisional excitation followed by fluorescence decay, radiative cascade processes, M-shell dielectronic recombination, Bremsstrahlung, and a new off-shell, quasi-resonant continuum dielectronic recombination process. We find that excitation fluorescence is the dominant process, with smaller contributions from the other radiative cascade processes as well as a continuous Bremsstrahlung background.     

Internal Rotation and Equilibrium Structure of the Bromonitromethane Molecule According to Gas Electron Diffraction Data and Quantum Chemical Calculations

The structure and internal rotation of the bromonitromethane molecule are studied using electron diffraction analysis and quantum chemical calculations. The electron diffraction data are analyzed within the models of a general intramolecular anharmonic force field and quantum chemical pseudoconformers to account for the adiabatic separation of a large amplitude motion associated with the internal rotation of the NO₂ group. The following experimental bond lengths and valence angles are obtained for the equilibrium orthogonal configuration of the molecule with C_s symmetry: r_e(N=O) = 1.217(5) Å, r_e(C–N) = 1.48(2) Å, r_e(C–Br) = 1.919(5) Å, ∠_еBr–C–N = 109.6(9)°, ∠_еO=N=O = 125.9(9)°. The equilibrium geometry parameters are in good agreement with CCSD(T)/cc-pVTZ calculations. Thermally averaged parameters are calculated using the equilibrium geometry and quadratic and cubic quantum chemical force constants. The barrier to internal rotation cannot be determined reliably based on the electron diffraction data used in this work. There is a 82% probability that the equilibrium configuration with orthogonal C–Br and N=O bonds is most preferable, and internal rotation barrier does not exceed 280 cm^-1, which agrees with CCSD(T)/cc-pVTZ calculations.     

Self-consistent molecular hartree—fock—slater calculations. IV. On electron densities,spectroscopic constants and proton affinities of some small molecules

The use of the Xα exchange approximation in calculations on small molecules is studied. Electron densities are very similar to Hartree—Fock densities, as judged from density difference maps. The statistical total energy, E_Xα, is used in order to calculate R_eB_e, ω₃ and D_e of a series of diatomic molecules. The agreement with experiment is again similar to that in Hartree—Fock calculations. Proton affinities can also be calculated very well. The Hartree—Fock—Slater and Hartree—Fock models show on the whole very analogous behaviour. These results are obtained by using accurate, unapproximated, potentials and densities.