José Paulo Santos

Ab initio and density functional calculations have been performed to study the benzyl azide, 2-, 3- and 4-methyl benzyl azides. Several molecular properties, such as conformational equilibrium, optimal geometry, and vibrational frequencies, have been computed for these molecules. Ionisation energies were also computed.

Ab initio and density functional calculations have been performed to study the benzyl azide, 2-, 3- and 4-methyl benzyl azides. Several molecular properties, such as conformational equilibrium, optimal geometry, and vibrational frequencies, have been computed for these molecules. Ionisation energies were also computed.

Wavelengths and oscillator strengths for all dipole-allowed fine-structure transitions in Zr III have been calculated within the Multi-Configuration Dirac-Fock method with QED corrections. These transitions are included in the spectrum of some chemically peculiar stars, like the B-type star Lupi observed by the Hubble space telescope. The results are compared to existing experimental and semi-empirical data.

Wavelengths and oscillator strengths for all dipole-allowed fine-structure transitions in Zr III have been calculated within the Multi-Configuration Dirac-Fock method with QED corrections. These transitions are included in the spectrum of some chemically peculiar stars, like the B-type star Lupi observed by the Hubble space telescope. The results are compared to existing experimental and semi-empirical data. Corr

The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCHNH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.

The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCHNH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.

In the present work we have calculated several relativistic transition probabilities for the F-like ions with 10 less-than-or-equals, slant Z less-than-or-equals, slant 49, in the framework of the Multi-Configuration Dirac–Fock method, for applications on laserphysics and astrophysics. The lines considered correspond to transitions between levels of 2p43s, 2p43p and 2p43d configurations. The spectral fine structure is taken into consideration and the results for individual lines are given.

The QED contribution to the energies of the circular (n, = n–1), 2n13, transitions have been calculated for several kaonic atoms throughout the periodic table, using the current world-average kaon mass. Calculations were done in the framework of the Klein-Gordon equation, with finite nuclear size, finite particle size, and all-order Uelhing vacuum polarization corrections, as well as Källén and Sabry and Wichmann and Kroll corrections. These energy level values are compared with other computed values. The circular transition energies are compared with available measured and theoretical transition energies. Electron screening is evaluated using a Dirac-Fock model for the electronic part of the wave function. The effect of electronic wave-function correlation is evaluated.Exo

The QED contribution to the energies of the circular (n, = n–1), 2n13, transitions have been calculated for several kaonic atoms throughout the periodic table, using the current world-average kaon mass. Calculations were done in the framework of the Klein-Gordon equation, with finite nuclear size, finite particle size, and all-order Uelhing vacuum polarization corrections, as well as Källén and Sabry and Wichmann and Kroll corrections. These energy level values are compared with other computed values. The circular transition energies are compared with available measured and theoretical transition energies. Electron screening is evaluated using a Dirac-Fock model for the electronic part of the wave function. The effect of electronic wave-function correlation is evaluated.

Energies of the circular (n, ℓ = n − 1) 1 less-than-or-equals, slant n less-than-or-equals, slant 20 levels have been calculated for hydrogenlike sigmonic atoms with 1 less-than-or-equals, slant Z less-than-or-equals, slant 92, using the current world average sigma mass, as well as the electronic shift in Σ− + Ne e− + nucleus systems, where Ne stands for the number of electrons. The electronic influence on sigmonic orbitals has also been investigated through the computation of the hyperfine structure and the anomalous Σ− magnetic moment effects in sigmonic Be 2p states.

Energies of the circular (n, ℓ = n − 1) 1 less-than-or-equals, slant n less-than-or-equals, slant 20 levels have been calculated for hydrogenlike sigmonic atoms with 1 less-than-or-equals, slant Z less-than-or-equals, slant 92, using the current world average sigma mass, as well as the electronic shift in Σ− + Ne e− + nucleus systems, where Ne stands for the number of electrons. The electronic influence on sigmonic orbitals has also been investigated through the computation of the hyperfine structure and the anomalous Σ− magnetic moment effects in sigmonic Be 2p states.Exo

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Energies of two-electron one-photon transitions from initial double K-hole states were computed using the Dirac–Fock model. The transition energies of competing processes, the Ka hypersatellites, were also computed. The results are compared with experiment and to other theoretical calculations.

The thermal decomposition of 2-azidoacetamide (N3CH2CONH2) has been studied by matrix-isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2, CH2NH, HNCO, CO, NH3, and HCN are observed as high-temperature decomposition products, while at lower temperatures, the novel imine intermediate H2NCOCHNH is observed in the matrix-isolation IR experiments. The identity of this intermediate is confirmed both by ab initio molecular orbital calculations of its IR spectrum and by the temperature dependence and distribution of products in the photoelectron spectroscopy (PES) and IR studies. Mechanisms are proposed for the formation and decomposition of the intermediate consistent both with the observed results and with estimated activation energies based on pathway calculations.

We present a systematic study of atomic binding energies, in the Dirac–Fock approximation, for the Lithium (3 electrons) to the Dubnium (105 electrons) isoelectronic series. In each series we have considered all atomic numbers from the one corresponding to the neutral atom up to Z=118. We have obtained the ground state configurations for several heavy ions with charge larger than one.

The relativistic version of the binary-encounter Bethe (BEB) model is used to calculate cross sections for K-shell ionization of atoms by electron impact. The BEB model requires only two atomic constants, the binding energy and kinetic energy of the K electrons. These constants are listed for carbon to antimony. Comparisons with available experimental data on N, O, Na, Al, Cl, Ca, Cu, Se and Sb show good agreement. The K-shell ionization cross sections for C, Mg, P, S, Cr, As and Cd are tabulated.

Energies of the [( n ,l= n -1),1= n =20] and the [( n ,l= n -2),2= n =20] levels have been calculated for several hydrogenlike kaonic atoms throughout the periodic table, using the current world average kaon mass. Calculations were done in the framework of the Klein–Gordon equation, with finite nuclear size and all-order vacuum polarization corrections.

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Ab initio calculations have been performed to study the methyl azidoformate (N3COOCH3) and the ethyl azidoformate (N3COOCH2CH3). Several molecular properties, such as conformational equilibrium, optimal geometry, and vibrational frequencies, have been computed for these molecules. Ionization energies based on Koopman's theorem were also computed.

Energies of two-electron one-photon transitions from initial double K-hole states and the transition energies of competing processes, namely K hyper-satellites, were computed for low-Z elements, using the multi-configuration Dirac–Fock method. Transition rates are also evaluated.

The triple-to-double ionization cross-section ratio of Li in the high-energy limit was computed in the sudden approximation with relativistic wave functions. Together with the calculated value of Dalgarno and Sadeghpour (Phys. Rev. A, 46 (1992) R3591), for the Li double-to-single ionization cross-section ratio, the value of 6.263x10-5 was obtained for the triple-to-single ionization cross-section ratio. This value is in full agreement with Wehlitz et al. experimental value of (6.38+-2.40)x10-5 obtained recently with synchrotron radiation (Phys. Rev. Lett., 81 (1998) 1813).

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We examine the most important processes leading to the creation of excited states from the ground configurations of Ar8+ to Ar16+ ions in an electron-cyclotron resonance ion source, which lead to the emission of K x-ray lines. Theoretical values for inner-shell excitation and ionization cross sections, including double KL ionization, transition probabilities and energies for the de-excitation processes, are calculated in the framework of the multi-configuration Dirac-Fock method. With reasonable assumptions about the electron energy distribution, a theoretical K x-ray spectrum is obtained, which reproduces very closely a recent experimental result.

Measurements of electron impact ionization of neutral Al, Ga, and In show large cross sections compared to other elements in the same rows of the periodic table. Semiempirical and classical calculations of direct ionization cross sections are all substantially smaller. Calculations by McGuire [Phys. Rev. A 26, 125 (1982)] for aluminum that include excitations to autoionizing 3s3p2 doublet levels are 2.5 times higher than experiment at the peak. We report the direct ionization cross sections based on the binary-encounter-Bethe model of Kim and Rudd [Phys. Rev. A 50, 3954 (1994)], which is an ab initio theory. We add the autoionization contribution using scaled plane-wave Born cross sections as recently developed by Kim [Phys. Rev. A 64, 032713 (2001)] for excitations to the first set of autoionizing levels. Dirac-Fock wave functions are used for the atomic structure. Our results are in excellent agreement with experimental values and support substantial contributions from excitation-autoionization to the total ionization cross sections for these elements. We also compare the total ionization cross section of boron to available theories, though no experimental data are available.

The determination of atomic masses from highly ionized atoms using Penning Traps requires precise values for electronic binding energies. In the present work, binding energies of several ions (from several elements) are calculated in the framework of two relativistic many-body methods: Relativistic Many-Body Perturbation Theory (RMBPT) and Multi-Configuration Dirac– Fock (MCDF). The ions studied in this work are: Cl (He and Li-like), Se (F and Ne-like), Cs (He, Be, Ne, Al, Cl, Ar, K, Kr, Xe-like and neutral Cs), Hg, Pb and U (Br and Kr-like). Some of them are presented in this paper. Cesium has been treated in more details, allowing for a systematic comparison between MCDF and RMBPT methods. The Cs ions binding energies allow for the determination of atomic Cs mass, which can be used in a QED-independent fine structure constant determination.