A sense of new beginnings in positron and positronium chemistry

Conclusion This has been the most future-oriented workshop in my memory. Many participants are thinking about the next experiments to perform, new phenomena to study, and new parameters to measure. We look forward to new optical correlations, both with exciting radiation and intrinsic fluorescence. We very badly need positron and positronium binding energies to atoms, molecules, and radicals. We very badly need work functions, band gaps and edges, and trap depths for positron and positronium in molecular liquids and solids. The binding energies of positronium itself in various molecular materials is an important and poorly understood quantity. New data presented at this workshop on the energy of positronium at its formation, and its thermalization time, are most significant,³ and we look forward to refinements in those measurements and in their interpretation. We need to understand the thermalization times of positrons much better than we do. The role of voids and/or surfaces in positronium formation needs to be illuminated, including numerical estimates and measurements for the cross section of this most important process.Finally, a note of thanks and appreciation to the hard-working organizers of this workshop, without whose selfless labors we would not have enjoyed the many benefits of talking face to face with our colleagues from far away.     

Theoretical study of positron scattering by group 14 tetra hydrides: A quantum mechanical approach

The present work provides a comprehensive set of positron impact scattering cross sections for group 14 tetrahydrides, namely, SiH₄, GeH₄, SnH₄, and PbH₄. The well‐established spherical complex optical potential and complex scattering potential‐ionization contribution methods are modified to incorporate positron scattering in the present work to calculate various cross sections. The positronium formation channel is adequately included through an improved inelastic threshold. The energy range chosen for the direct ionization cross section is from the respective ionization potential (I) of the molecule to 5 keV. Likewise, positronium formation and total ionization cross sections are reported from the positronium formation threshold to 300 eV and 5 keV, respectively, and the total cross section is computed for an extensive energy range of 1 eV to 5 keV. The positron impact total cross section for stannane molecule is computed for the first time. A characteristic valley is observed in the total cross sections with minima close to the positronium formation threshold. Further increase of cross section signifies the opening of inelastic channels especially positronium formation. In general, a reasonable agreement is found between the present results and other comparisons, wherever available. Furthermore, this is the first report of the inelastic cross sections (direct ionization, positronium formation, and total ionization) for the present set of targets.     

Exotic Clusters Formed by Electrons and Positrons: Approximate Calculations of Binding Energies and Bonding Capabilities of Positronium Atom and Dipositronium and Positronium Hydride Molecules Based on Their Hydrogen Analogs

A simple method is presented which allows us to estimate the binding energies and bonding capabilities of exotic species formed by electrons, positrons, and protons, namely, the positronium atom (Ps) and the dipositronium (Ps₂) and positronium hydride (PsH) molecules. These exotic species are in fact the simplest clusters formed by the aforementioned fundamental particles and antiparticles. The simple Bohr atom model for hydrogen is extended to calculate the binding energies and radii of atomic orbitals of the Ps atom, as well as its atomic and covalent sizes and electronegativity. Based on these properties, the bond lengths and bond energies, including the covalent and ionic contributions, of the Ps₂ and the PsH molecules can be estimated from the corresponding (known) values of the dihydrogen molecule (H₂) using a Hückel-like molecular orbital calculation.     

Lineshape studies of deconvoluted spectra of annihilation radiation in neopentane solutions of some organic iodides

The inhibition of positronium formation in neopentane caused by the addition of some organic iodides through the measurements of the energy spectra of Doppler-broadened annihilation radiation has been studied by using a deconvolution technique. The observed results could be interpreted by the reaction or the selective interaction of the positrons or the hot positronium atoms with the solute molecules. The observed change of the momentum distribution curve by the addition of the organic iodides can be explained consistently by these interpretations.     

Present and future positron-molecular scattering experiments

Progress to date (June, 1999) of the Oak Ridge positron scattering project is reviewed. Results from our positron time-of-flight mass spectrometer include ionization and fragmentation of some halomethanes, positronium formation below the threshold for double ionization of Ne and the heavier noble gases, and the production of HeH⁺ by positron impact on mixtures of He and H₂. New directions for future experimental work are discussed. These entail the construction and testing of a new spectrometer which measures both the masses and recoil energies of charged products, including secondary electrons. We hope to use an intense positron beam, such as the one at Lawrence Livermore National Laboratory or a similar beam, as the ionizing agent for the new spectrometer, which contains a pulsed supersonic molecular beam. With such an instrument, a range of new phenomena can be studied.     

Microheterogeneity in mixtures of benzene with alcohols and hydrocarbons: Positron annihilation and molecular light scattering

Experimentally measured concentration dependences of the probability of positronium formation and the intensity of molecular light scattering in binary benzene-ethanol and benzene-cyclohexane mixtures were analyzed. The observed behavior was explained by association of molecules. Arguments are presented in favor of the formation in benzene-ethanol mixtures of alcohol associates capable of capturing and solvating quasi-free electrons formed in the tracks of high-energy positrons during their passage through the mixture. As the concentration of associates rises, the positronium formation rate decreases while the intensity of the light scattered by them increases. The mean size and lifetime of the associates were evaluated. It was established that, in benzene-ethanol and benzene-cyclohexane mixtures at temperatures below room temperature, benzene associates are formed.     

Positron binding energies for alkali hydrides

Ab initio multireference single- and double-excitation configuration interaction (MRD-CI) calculations are carried out to study the interactions of positrons with the members of the alkali hydride class of molecules. A new computer program has been constructed for this purpose that makes use of the Table-Direct-CI method for construction of the required Hamiltonian matrixes and electronic/positronic wave functions. The calculations indicate that the binding energy (positron affinity PA) of a single positron to these systems increases by an increment of 0.2-0.3 eV as the atomic number of the alkali atom is increased. It is found that the positron prefers a location in the more electronegative regions of such molecules, similarly as has been found in earlier calculations for the urea and acetone molecules. The positron orbital itself possesses a diffuse charge distribution with relatively small expectation values of the kinetic energy in all four systems considered. Each of the four positronic molecules is stable with respect to formation of either positronium (Ps) or HPs according to the present calculations. Relatively large changes in the equilibrium bond distance of the hydrides occur as a result of the positron interaction. The importance of bond dipole moments in producing the binding of positrons to molecules is discussed, as well as the role that the electronegativity of the constituent atoms plays in determining the magnitude of the PA for a given system.     

Evaluation of elastic‐scattering cross sections for electrons and positrons over a wide energy range

Quantification of surface‐ and bulk‐analytical methods, e.g. Auger‐electron spectroscopy (AES), X‐ray photoelectron spectroscopy (XPS), electron‐probe microanalysis (EPMA), and analytical electron microscopy (AEM), requires knowledge of reliable elastic‐scattering cross sections for describing electron transport in solids. Cross sections for elastic scattering of electrons and positrons by atoms, ions, and molecules can be calculated with the recently developed code ELSEPA (Elastic Scattering of Electrons and Positrons by Atoms) for kinetic energies of the projectile from 10 eV to 50 eV. These calculations can be made after appropriate selection of the basic input parameters: electron‐density distribution, a model for the nuclear‐charge distribution, and a model for the electron‐exchange potential (the latter option applies only to scattering of electrons). Additionally, the correlation‐polarization potential and an imaginary absorption potential can be considered in the calculations. We report comparisons of calculated differential elastic‐scattering cross sections (DCSs) for silicon and gold at selected energies (500 eV, 5 keV, 30 keV) relevant to AES, XPS, EPMA, and AEM, and at 100 MeV as a limiting case. The DCSs for electrons and positrons differ considerably, particularly for medium‐ and high‐atomic‐number elements and for kinetic energies below about 5 keV. The DCSs for positrons are always monotonically decreasing functions of the scattering angle, while the DCSs for electrons have a diffraction‐like structure with several minima and maxima. A significant influence of the electron‐exchange correction is observed at 500 eV. The correlation‐polarization correction is significant for small scattering angles at 500 eV, while the absorption correction is important at energies below about 10 keV. Copyright © 2005 John Wiley & Sons, Ltd.     

Positronium hydride formation in collisions of positrons with molecular hydrogen

Summary The feasibility of observing the threshold for the formation of positronium hydride, PsH, in collisions of low-energy positrons with hydrogen molecules in a mass spectrometric application is considered. The expected count rate of the signature ion H⁺ using existing positron beams depends upon the cross section for a dissociative attachment reaction. The estimation of this cross section relies on knowledge of certain potential energy curves and leptonic wave functions. This knowledge does not yet exist. The curves are roughly estimated by considering the binding of a positron to the ionicB state of H₂. Methods of calculating the wave functions are briefly considered.A preliminary version was presented at the Third International Workshop on Positron and Positronium Chemistry, Milwaukee, July 1990 (Ref. [1])     

Multireference configuration interaction calculations for positronium halides

Multireference configuration interaction (MRCI) calculations of the positronium halides, PsF, PsCl, PsBr, and PsI, are carried out, to give positron ionization energies, positronium binding energies, and two-photon annihilation rates. All CI calculations consider only valence correlation effect with a frozen-core approximation, and use the orbitals with angular momentum up to 8. To incorporate the effects of many-body correlations in the energies and two-photon annihilation rates, the MRCI calculations are repeated with increasing reference configurations, and the full CI limits of these energies and annihilation rates are estimated. The contribution from orbitals having angular momentum greater than 8 to those values is also estimated. Relative to our previous single reference CI calculations, many-body correlation effects significantly increase the positron ionization energies, positronium binding energies, and two-photon annihilation rates. The structures of the positronium halides are also discussed.     

Absolute partial cross sections and kinetic energy analysis for the electron impact ionization of ethylene

We present absolute partial electron impact ionization cross sections for ethylene in the electron energy range between threshold and 1000 eV measured with a two sector field double focusing mass spectrometer. Ion kinetic energy distribution functions have been measured at all electron energies by applying a deflection field method. Multiplication of the measured relative cross sections by the appropriately determined discrimination factors lead to accurate relative partial cross sections. Normalization of the sum of the relative partial cross sections to an absolute total cross section gives absolute partial cross section values. The initial kinetic energy distributions of several fragment ions show the presence of two or more contributions that exhibit different electron energy dependencies. Differential cross sections with respect to the initial kinetic energy of the ions are provided and are related to specific ion production channels. The electron threshold energies for the direct and numerous other dissociative ionization channels are determined by quantum chemical calculation and these allow the determination of the total kinetic energy release and the electron energy loss for the most prominent dissociative ionization channels.     

Polarisation potentials for positron-molecule scattering processes

A new form of a local, model polarisation-correlation potential obtained via Density Functional Theory (DFT) is proposed for the treatment of positron scattering from H₂ and N₂ molecules at energies below the threshold of positronium formation. The derivation of the potential is briefly discussed and its relative importance for the elastic channels of the scattering process is analysed in detail. Final elastic cross sections, rotationally summed, are compared with experiments and with existing theoretical results. They are found to agree reasonably well with measurements and suggest the present model as a useful, and simple, method for treating short-range correlation forces in positron scattering calculations for molecular systems.     

Localized versus delocalized excitations just above the 3d threshold in krypton clusters studied by Auger electron spectroscopy

We present Auger spectroscopy studies of large krypton clusters excited by soft x-ray photons with energies on and just above the 3d(52) ionization threshold. The deexcitation spectra contain new features as compared to the spectra measured both below and far above threshold. Possible origins of these extra features, which stay at constant kinetic energies, are discussed: (1) normal Auger process with a postcollision interaction induced energy shift, (2) recapture of photoelectrons into high Rydberg orbitals after Auger decay, and (3) excitation into the conduction band (or "internal" ionization) followed by Auger decay. The first two schemes are ruled out, hence internal ionization remains the most probable explanation.     

Investigation of the near surface region of chemically treated and Al-coated PMMA by Doppler-broadening spectroscopy

The positronium formation is studied in the near surface region of Polymethylmethacrylate (PMMA), which was treated with isopropanol and acetone by energy dependent Doppler-broadening spectroscopy. In addition, the variation of Ps-formation was investigated at aluminium-coated PMMA. The coincident DB (CDB) spectra reveal the fraction of positrons, which annihilate in the aluminium. All measurements were performed with mono-energetic positrons up to an energy of 31 keV at the CDB-spectrometer at the new positron beam facility NEPOMUC at FRM II.     

The prediction of atomic kinetic energies from coordinates of surrounding atoms using kriging machine learning

A novel design of a next-generation force field considers not only the electronic inter-atomic energy but also intra-atomic energy. This strategy promises a faithful mapping between the force field and the quantum mechanics that underpins it. Quantum chemical topology provides an energy partitioning in which atoms have well-defined electronic kinetic energies, and we are interested in capturing how they respond to changes in the positions of surrounding atoms. A machine learning method called kriging successfully creates models from a training set of molecular configurations that can then be used to predict the atomic kinetic energies occurring in previously unseen molecular configurations. We present a proof-of-concept based on four molecules of increasing complexity (methanol, N-methylacetamide, glycine and triglycine). We test how well the atomic kinetic energies can be modelled with respect to training set size, molecule size and elemental composition. For all atoms tested, the mean atomic kinetic energy errors fall below 1.5 kJ mol^?1, and far below this in most cases. This represents errors all under 0.5 % and thus the kinetic energies are well modelled using the kriging method, even when using modest-to-small training set sizes.     

The vacancy formation energy in crystalline adamantane determined by position annihilation techiniques

The injection of positrons into crystalline adamantane results in the formation of positronium (Ps). At temperatures T> 400 K the mean lifetime of the long-lived ortho-positronium exhibits a sigmoidal increase with temperature characteristic of the trapping of this species in thermally created defects. The variation is well described by the trapping model usually applied to the trapping of positrons in defects in metals. The formation energy of the defects which trap ortho-Ps is estimated at E_f^v = 70 ± 10 kJ mol^-1 (0.73 ± 0.1 eV). This value is in good agreement with estimates of the formation energy of lattice vacancies in adamantane derived from self-diffusion studies.     

Positron interactions with overlayers of oxygen on GaAs(100)

The positron work-function, re-emission yield, and positronium fraction of an n-doped GaAs(100) surface were measured as a function of oxygen exposure. The energy distribution of positrons observed to be re-emitted indicated that the clean and oxygen exposed n-doped GaAs(100) surfaces had negative positron work-functions. The fraction of incident positrons re-emitted as bare positrons, (Y), was found to increase and the fraction re-emitted as positronium, (f_Ps), to decrease with increasing oxygen exposure. This suggests that surface modified GaAs may be useful as a contact material in the fabrication of GaAs based FAMs.     

Photoionization dynamics in pure helium droplets

The photoionization and photoelectron spectroscopy of pure He droplets were investigated at photon energies between 24.6 eV (the ionization energy of He) and 28.0 eV. Time-of-flight mass spectra and photoelectron images were obtained at a series of molecular beam source temperatures and pressures to assess the effect of droplet size on the photoionization dynamics. At source temperatures below 16 K, where there is significant production of clusters with more than 10(4) atoms, the photoelectron images are dominated by fast electrons produced via direct ionization, with a small contribution from very slow electrons with kinetic energies below 1 meV arising from an indirect mechanism. The fast photoelectrons from the droplets have as much as 0.5 eV more kinetic energy than those from atomic He at the same photon energy. This result is interpreted and simulated within the context of a "dimer model", in which one assumes vertical ionization from two nearest-neighbor He atoms to the attractive region of the He2+ potential energy curve. Possible mechanisms for the slow electrons, which were also seen at energies below IE(He), are discussed, including vibrational autoionizaton of Rydberg states comprising an electron weakly bound to the surface of a large HeN+ core.     

Wavelength-dependent fragmentation in resonance-enhanced multiphoton ionization mass spectrometry

Wavelength-dependent effects in the resonance-enhanced multiphoton ionization/fragmentation mass spectra of p-chloroaniline and diphenyl ether are presented. For both molecules, the formation of low-energy fragments can be discriminated against in favor of higher-energy fragments by using ‘low’-energy radiation (290 nm region) for ionization/fragmentation. The same low-energy fragments become dominant when higher-energy radiation (266 nm) is used. This unique behavior is explained in terms of the narrow distribution of parent ion internal energies created through resonance-enhanced multiphoton ionization/fragmentation and the competing kinetic processes accessed by the parent ion as it absorbs each successive photon.     

Positronium formation at low temperatures: the role of trapped electrons

Measurements have been carried out of electron spin densities (by electron spin resonance technique) and positronium (Ps) formation probability as functions of Co-60 γ-irradiation dose in poly(methyl methacrylate) and linear poly(ethylene) at 77 K. We observe a linear relationship between the enhancement of the Ps formation and the density of trapped electrons in both polymers. This clear correlation strongly supports the previous suggestion by the authors that the increase in Ps formation with time (that has been observed at low temperatures for a number of polymers) can be explained as a reaction of free positrons with trapped electrons produced by the previously injected positrons.