Electron impact ion fragmentation of a laser vibrationally excited HF nozzle beam

The electron impact ion fragmentation of a hydrogen fluoride molecular beam excited by a cw HF laser into the v = 1 vibrational level has been investigated with a quadrupole mass spectrometer. The ratio of the F⁺ to HF⁺ ion signals is found to increase linearly with increasing degree of excitation and decreasing electron energy. The results are interpreted in terms of the Franck—Condon overlap with the ionic potential curves. These direct quantitative measurements demonstrate the use of a mass spectrometer as a probe of the degree of vibrational excitation of HF in a molecular beam.     

Angular momentum coherences of helium atoms excited by proton impact

Using electric-field anticrossing techniques, we investigated the coherent excitation ofn=5–8 He I states with different orbital angular momenta by proton impact. These measurements give strong evidence that saddle dynamics of H ₂ ⁺ -like systems are well suited for describing the final phase of 12.5 keV H⁺-He collisions. We conclude that, besides electron promotion via the 2pσ orbital, the collision system undergoes diabatic 1sσ–3dσ transitions during the close encounter and present an explanation of the electric dipole moments measured for excitation of H(n=2) states by H⁺-He and H-He collisions.     

Electron transfer from laser excited rydberg atoms to molecules. Absolute rate constants at low and intermediate principal quantum numbers

Using mass spectrometric detection of positive and negative ions, we have investigated ionizing reactions of Ne(ns,nd) Rydberg atoms, efficiently excited by resonant two-photon excitation of metastable Ne(3s ³ P ₂) atoms, with electron attaching moleculesBC (BC=SF₆, CCl₄, CS₂, O₂) at thermal collision energies. Absolute rate constants have been determined in the range of low and intermediate principal quantum numbersn(5≦n?30) by utilizing the photoionization signal caused by room temperature black-body radiation and the loss of Ne(3s ³ P ₂) atoms, associated with the laser excitation. Substantially differentn-dependences of the electron transfer cross section have been found for the larger molecules (BC = SF₆, CCl₄) and the smaller molecules (BC = CS₂, O₂). Simple model calculations have been performed to gain new insight into the dynamics of the electron transfer process; forBC = SF₆, our results at lown(5 ≦n ≦ 10) suggest that internal energy conversion in the Coulombic complex Ne⁺ — SF ₆ ^? is important for the formation of the detected ions.     

Formation of water and ammonia cluster anions by electron transfer from laser excited Rydberg atoms

Using a laser excited Rydberg atomic beam as a very low energy (10-270 meV) electron source, we have investigated the experimental conditions for observation of water (from dimer to 40-mer) and ammonia cluster anions. From simple model calculations, estimates of the small water cluster adiabatic electron affinities have been determined as well as the orders of magnitude of autodetachment lifetimes and attached electron critical energies.     

Translational energy distribution of excited deuterium atoms produced by controlled electron impact on D2

The Balmer-β line of the excited deuterium atom [D*(n = 4)] produced in e—D₂ collisions has been measured at high resolution (0.029–0.033 Å) and at various electron energies (17–100 eV). The translational energy distribution of D*(n = 4) has been calculated from analysis of its Doppler line shape. The distribution of D* has three major components as in the case of H*(n = 4) from H₂ reported in our previous paper. Their peaks lie at about 0, 6 and 8 eV. The excitation function of D* is found to have two thresholds at 17.4 and 26.4 eV. The second component of D* has a larger translational energy and a higher threshold than those of the corresponding component of H*. These results indicate that the contribution from the lowest doubly excited state, ¹Σ_g⁺(2pσ_u)², is much smaller for D₂ than that for H₂.     

Electron microscopic study of barium hexaaluminates

The crystallographic relation between phase I and phase II of barium hexaaluminates, which were conventionally considered as the single compound “barium hexaaluminate (BaAl₁₂O₁₉),” was investigated using principally the electron diffraction method. Phase I (Ba_0.79Al_10.9O_17.14) was found to have β-alumina type structure with space group $\text{P6}{}_3\text{mmc}$. On the other hand, phase II (Ba_2.34Al_21.0O_33.84) exhibited an a√3 × a√3 superstructure, which is probably due to the ordering of excess Ba ions within BaO layers. Possible structure models of both phases are presented.     

Analysis of collisional alignment and orientation studied by scattering of spin-polarized electrons from laser excited atoms

A general framework using density matrices is developed for the analysis of atomic excitation by spin-polarized electrons. This framework is applied to the specific case of the 3S _1/2→3P _3/2 transition in Na, as studied by the time-reversed, superelastic process. The scattering is characterized in terms of physical parameters describing the collisionally excitedp-state, i.e., its angular momentum (L _⊥), linear polarization (P _lin), and alignment angle (γ), with these parameters defined separately for singlet and triplet excitation. An expression for the scattering intensity is derived which is valid for arbitrary electron polarization and atomic state preparation. Specific examples are discussed with a view toward complete determination of the relevant scattering amplitudes and phases. Recent experimental results are reevaluated for comparison with theoretical calculations, and suggestions are made for future experiments.     

Microwave ionization of highly excited hydrogen atoms

Within a 1-dimensional model we calculate quantum mechanically the probability to ionize a highly excited hydrogen atom by a monochromatic microwave field. Based on a detailed analysis of the ionization process we developed a computational scheme as well as a simple physical framework which are presented and discussed. Our calculations are in good agreement with the experimental results. We show that the experimentally measured ionization thresholds are due to a sharp transition between two localization regimes and that recently measured structures below the classical chaos border are due to unresolved clusters of Floquet pseudo crossings. We propose an experimental method by which one could measure the distance and distribution of crossing Floquet eigenvalues.     

Electron emission from naphthacene crystal due to the impact of argon and krypton metastable atoms

Energy distributions of electrons emitted from polycrystalline naphthacene due to the impact of metastable argon or krypton atoms were measured. The energy distribution peaks, except for large peaks appearing near zero eV, correspond to the kinetic energies estimated from photoelectron spectra on the assumption that the excitation energies of the metastable atoms are transferred to the electrons in the valence bands. The results are interpreted as the occurrence of Penning ionization (Auger de-excitation) on the naphthacene surface.     

Activation of dimethyl ether with barium and strontium atoms

Organometallic compounds are produced when barium and strontium atoms are cocondensed with dimethyl ether at ?196°C; hydrolysis of the cocondensation products from both reactions yields mainly C₁—C₈ alkanes, alkenes, and alkynes.     

Accurate time-resolved laser spectroscopy on lithium atoms

The lifetime of the lithium 2p ² P states has been measured with high accuracy using the delayed coincidence technique with a continuous mode-locked dye laser as the source of the excitation light. The value 27.22 (0.20) ns was obtained. In addition, the hyperfine structure of the⁷Li 2p ² P _3/2 state, which can normally scarcely be resolved, has been studied by recording the slow quantum beats at zero field and the very fast beats in the Paschen-Back regime. New accurate values for the²³Na 3p ² P _3/2 state hyperfine structure constants are also presented.     

Accurate time-resolved laser spectroscopy on silver atoms

The lifetimes of the silver 5p ² P states have been measured with high accuracy by time-resolved laser spectroscopy using the delayed coincidence technique. Also, the hyperfine structure of¹⁰⁷Ag and¹⁰⁹Ag in these two states has been studied by observing quantum beats.     

The deposition of energy from reactions of laser excited atoms: Strontium 3P1 with hydrogen halides

The chemical reactions of laser excited Sr^*(³P₁) with HF and HCl are studied in a beam gas arrangement with LlF detection. This is the first experiment reported where both the specific electronic state of the reactant is laser prepared and the specific vibrational states of the products are laser detected. The results show that a large fraction of the available energy is released into vibration of SrX.     

Molecular orbitals for excited states of atoms and molecules

A method is described for calculating SCF wavefunctions for excited electronic states of atoms and molecules. The orthogonality conditions with the ground state wavefunction and the underlying excited states wavefunctions are introduced in the SCF process in a simplified form.     

Pseudomolecular atoms: geometry of two-electron intrashell excited states

Supermultiplet patterns indicating pronounced collective motion of electrons are prominent among intrashell excited states of helium or alkaline earth atoms. Many aspects of these patterns have previously been discussed in terms of an empirical rovibrator model, e-core-e, analogous to alinear triatomic molecule. However, this has appeared incompatible with a dimensional scaling treatment that predicts pseudomolecular features and relates properties of some excited states to the ground state, but corresponds to abent equilibrium geometry. We examine both the full two-electron Hamiltonian, including angular momentum, and a prototype model for angular correlation which restricts the two particles to the surface of a sphere. By virtue of the boundary conditions imposed by the Jacobian volume element, we find that alinear equilibrium geometry is not allowed. If the Hamiltonian is transformed to reduce the Jacobian to unity, an infinite barrier appears in the effective potential when the electrons are 180° apart and equidistant from the nucleus. We find the supermultiplet patterns, including some “antimolecular” features, are consistent with a floppy butbent geometry, anasymmetric rotor model. The most probable interelectron angle ? _m varies markedly with the principal quantum number and also with the space-quantization of the angular momentum with respect to body-fixed axes.     

Electron pair correlation in atoms and molecules

Accurate methods for computing energies and electronic properties of atoms and molecules have been derived from direct treatment of localized pairs of electrons. The conceptual development and implementation of such methods is reviewed.     

Relative spatial profiles of barium ion and atom in the argon inductively coupled plasma as obtained by laser excited fluorescence

Relative ionic and atomic fluorescence profiles for barium have been obtained in an argon inductively coupled plasma by exciting different transitions with a nitrogen-laser pumped tunable dye laser and measuring the resulting fluorescence pulses with a boxcar averager. Spatially resolved profiles are directly obtained without the need of an Abel inversion procedure, with a volume resolution of approximately 0.2 mm³. The profiles are given along the excitation axis as well as along the observation axis, for different heights above the coil and different input powers. At low heights, the ion profile resembles a hollow pencil with a typical double-peaked, asymmetric distribution, while the atom profile seems to be complementary to the ion profile. Some scatter from water is also evident at low heights.