One-electron capture with simultaneous ionization in Cq+, Oq+ (q=1-4)-Ar collisions

The ratios R-k1 of k-fold to single ionization of the target atom with simultaneous one-electron capture by the projectile have been measured for 15-480 keV/u (nu(p) = 0.8-4.4 a.u.) collisions of Cq+, Oq+ (q=1-4) with Ar, using time-of-flight techniques which allowed the simultaneous identification of the final charge state of both the low-velocity recoil ion and the high-velocity projectile for each collision event. The present ratios are similar to those for He+ and He2+ ion impact. The energy dependence of R-k1 shows a maximum at a certain energy, E-max. which approximately conforms to the q(1/2)-dependence scaling. For a fixed projectile state, the ratios R-k1 also vary strongly with outgoing reaction channels. The general behavior of the measured data can be qualitatively analyzed by a simple impact-parameter, independent-electron model. (C) 2009 Elsevier B.V. All rights reserved.

L-shell ionization accompanied by one-electron capture in Cq+, Oq+ (q=2,3)-Ne collisions

The L-shell ionization processes of a Ne gas target associated with single-electron capture by bombardment of Cq+ and Oq+ (q=2,3) are investigated using the projectile-recoil-ion coincidence method in the energy range from 80 to 400 keV/u (v(p)=1.8-4 a.u.). The cross-section ratios (R-k1) of k-fold ionization to single capture are compared with the results for He2+-Ne collisions by Dubois [Phys. Rev. A 36, 2585 (1987)]. All the velocity dependences are quite similar. The ratios increase as the projectile energy increases in the lower-energy region, reach the maxima for projectile energies around E-max=160q(1/2) keV/u, and then decrease at higher energies. These results qualitatively agree with our calculations in terms of the Bohr-Lindhard model within the independent-electron approximation.

Reactions of One-Electron-Oxidized Methionine with Oxygen: An ab initio study

A one-electron oxidation of a methionine residue is thought to be a key step in the neurotoxicity of the beta amyloid peptide of Alzheimer's disease. The chemistry of the radical cation of N-formylmethioninamide (11+) and two model systems, dimethyl sulfide (1+) and ethyl methyl sulfide (6+), in the presence of oxygen have been studied by B3LYP/6-31G(d) and CBS-RAD calculations. The stable form of 11+ has a three-electron bond between the sulfur radical cation and the carbonyl oxygen atom of the i - 1 residue. The radical cation may lose a proton from the methyl or methylene groups flanking the oxidized sulfur. Both 11+ and the resultant C-centered radicals may add oxygen to form peroxy radicals. The calculations indicate that unlike C-centered radicals the sulfur radical cation does not form a covalent bond to oxygen but rather forms a loose ion-induced dipole complex with an S-O separation of about 2.7 Å, and is bound by about 13 kJ mol-1 (on the basis of 1+ + O2). Direct intramolecular abstraction of an H atom from the C site is unlikely. It is endothermic by more than 20 kJ mol-1 and involves a high barrier (G = 79 kJ mol-1). The -to-S C-centered radicals will add oxygen to form peroxy radicals. The OH BDEs of the parent hydroperoxides are in the range of 352-355 kJ mol-1, similar to SH BDEs (360 kJ mol-1) and C-H BDEs (345-350 kJ mol-1). Thus, the peroxy radicals are oxidizing species comparable in strength to thiyl radicals and peptide backbone C-centered radicals. Each peroxy radical can abstract a hydrogen atom from the backbone C site of the Met residue to yield the corresponding C-centered radical/hydroperoxide in a weakly exothermic process with modest barriers in the range of 64-92 kJ mol-1.

Combined R-matrix eigenstate basis set and finite-difference propagation method for the time-dependent Schrodinger equation: The one-electron case

In this work we present the theoretical framework for the solution of the time-dependent Schrödinger equation (TDSE) of atomic and molecular systems under strong electromagnetic fields with the configuration space of the electron’s coordinates separated over two regions; that is, regions I and II. In region I the solution of the TDSE is obtained by an R-matrix basis set representation of the time-dependent wave function. In region II a grid representation of the wave function is considered and propagation in space and time is obtained through the finite-difference method. With this, a combination of basis set and grid methods is put forward for tackling multiregion time-dependent problems. In both regions, a high-order explicit scheme is employed for the time propagation. While, in a purely hydrogenic system no approximation is involved due to this separation, in multielectron systems the validity and the usefulness of the present method relies on the basic assumption of R-matrix theory, namely, that beyond a certain distance (encompassing region I) a single ejected electron is distinguishable from the other electrons of the multielectron system and evolves there (region II) effectively as a one-electron system. The method is developed in detail for single active electron systems and applied to the exemplar case of the hydrogen atom in an intense laser field.

Quantum kinematics of Fermi-Dirac vacuum-plus-one-electron problem

Following Weisskopf, the kinematics of quantum mechanics is shown to lead to a modified charge distribution for a test electron embedded in the Fermi-Dirac vacuum with interesting consequences.

Part I. Approximate Hartree-Fock wavefunctions one-electron properties and electronic structure of the water molecule. Part II. Perturbation-variational calculation of the nuclear spin-spin isotope coupling constant in HD

Part I

Several approximate Hartree-Fock SCF wavefunctions for the ground electronic state of the water molecule have been obtained using an increasing number of multicenter s, p, and d Slater-type atomic orbitals as basis sets. The predicted charge distribution has been extensively tested at each stage by calculating the electric dipole moment, molecular quadrupole moment, diamagnetic shielding, Hellmann-Feynman forces, and electric field gradients at both the hydrogen and the oxygen nuclei. It was found that a carefully optimized minimal basis set suffices to describe the electronic charge distribution adequately except in the vicinity of the oxygen nucleus. Our calculations indicate, for example, that the correct prediction of the field gradient at this nucleus requires a more flexible linear combination of p-orbitals centered on this nucleus than that in the minimal basis set. Theoretical values for the molecular octopole moment components are also reported.

Part II

The perturbation-variational theory of R. M. Pitzer for nuclear spin-spin coupling constants is applied to the HD molecule. The zero-order molecular orbital is described in terms of a single 1s Slater-type basis function centered on each nucleus. The first-order molecular orbital is expressed in terms of these two functions plus one singular basis function each of the types e^-r/r and e^-r ln r centered on one of the nuclei. The new kinds of molecular integrals were evaluated to high accuracy using numerical and analytical means. The value of the HD spin-spin coupling constant calculated with this near-minimal set of basis functions is J_HD = +96.6 cps. This represents an improvement over the previous calculated value of +120 cps obtained without using the logarithmic basis function but is still considerably off in magnitude compared with the experimental measurement of J_HD = +43 0 ± 0.5 cps.

Energy-level shifts of a stationary hydrogen atom in a static external gravitational field with Schwarzschild geometry

he first order perturbations of the energy levels of a stationary hydrogen atom in a static external gravitational field, with Schwarzschild metric, are investigated. The energy shifts are calculated for the relativistic 1S, 2S, 2P, 3S, 3P, 3D, 4S, 4P, 4D, and 4F levels. The results show that the energy-level shifts of the states with total angular momentum quantum number 1/2 are all zero, and the ratio of absolute energy shifts with total angular momentum quantum number 5/2 is 145. This feature can be used to help us to distinguish the gravitational effect from other effects.

Double proton transfer and one-electron oxidation behaviors in double H-bonded glycinamide-formamidine complex and comparison with biological base pair

The behaviors of double proton transfer (DPT) occurring in a representative glycinamide-formamidine complex have been investigated employing the B3LYP/6-311++G** level of theory. Computational results suggest that the participation of a formamidine molecule favors the proceeding of the proton transfer (PT) for glycinamide compared with that without mediator-assisted case. The DPT process proceeds with a concerted mechanism rather than a stepwise one since no zwitterionic complexes have been located during the DPT process. The barrier heights are 14.4 and 3.9 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 3.1 and 2.9 kcal/mol to 11.3 and 1.0 kcal/mol with further inclusion of zero-point vibrational energy (ZPVE) corrections, where the lower reverse barrier height implies that the reverse reaction should proceed easily at any temperature of biological importance. Additionally, the one-electron oxidation process for the double H-bonded glycinamide-formamidine complex has also been investigated. The oxidated product is characterized by a distonic radical cation due to the fact that one-electron oxidation takes place on glycinamide fragment and a proton has been transferred from glycinamide to formamidine fragment spontaneously. As a result, the vertical and adiabatic ionization potentials for the neutral double H-bonded complex have been determined to be about 8.46 and 7.73 eV, respectively, where both of them have been reduced by about 0.79 and 0.87 eV relative to those of isolated glycinamide due to the formation of the intermolecular H-bond with formamidine. Finally, the differences between model system and adenine-thymine base pair have been discussed briefly.

Accurate computational methods for two-electron atom-laser interactions

We discuss the application of quantitatively accurate computational methods to the study of laser-driven two-electron atoms in short intense laser pulses. The fundamental importance of such calculations to the subject area is emphasized. Calculations of single- and double-electron ionization rates at 390 nm are presented. (C) 2001 Optical Society of America.

Collision mechanisms in one-electron capture by slow H and He- like ions of C, N and O in H and H-2

Translational energy spectroscopy (TES) has been used to study state-selective one-electron capture by H and He-like ions of C, N and O in both H and H-2 within the range 250-900 eV amu(- 1). The main collision mechanisms leading to state-selective electron capture have been identified, their relative importance assessed and compared, where possible, with theoretical predictions and with any previous measurements based on photon emission spectroscopy. For one-electron capture in H-2, the relative importance of contributions from non- dissociative and dissociative capture as well as from two- electron capture into autoionizing states is found to be strikingly different for the cases considered. Our TES measurements in atomic hydrogen provide an important extension of previous measurements to energies below 1000 eV amu(-1) and show that, as the impact energy decreases, electron capture becomes more selective until only a single n product channel is significant. These product main channels are well described by reaction windows calculated using a Landau-Zener approach. However, the same approach applied to the more complex energy- change spectra observed in H-2 is found to be less successful.

State-selective one-electron capture by slow state-prepared N2+(P-2) ground-state ions in collisions with hydrogen atoms

The technique of double translational energy spectroscopy.(DTES), recently successfully developed in this laboratory for use with targets of atomic hydrogen, has been used to study one-electron capture by ground-state N2+(2s22p)(2)p(0) ions in collisions with hydrogen atoms at energies within the range 0.8-6.0 keV. Cross sections for the formation of the main excited product channels have been determined. The measurements allow a re-evaluation of our previous TES measurements carried out with N2+ primary beams containing an admixture of metastable N2+(2s2p2)(4)p ions. The main findings of these earlier measurements are confirmed and the DTES measurements now remove any ambiguity in interpretation of the experimental data. While recent theoretical studies correctly predict the two main N+ D-3(0) and P-3(0) product channels, the quantitative agreement with experiment is only partially satisfactory.