José Paulo Santos

n/a

Radiationless transition rates to L1 vacancy states have been calculated ab initio in the Dirac-Fock approximation. The calculations include quantum-electrodynamic corrections. Results in the jj coupling scheme for all possible L1 transitions are tabulated for elements Yb and Hg.

Total electronic correlation corrections to the binding energies of the isoelectronic series of beryllium, neon, magnesium and argon, are calculated in the framework of relativistic multiconfiguration Dirac-Fock method. Convergence of the correlation energies is studied as the active set of orbitals is increased. The Breit interaction is treated fully self-consistently. The final results can be used in the accurately determination of atomic masses from highly charged ions data obtained in Penning-trap experiments.

Total electronic correlation corrections to the binding energies of the isoelectronic series of beryllium, neon, magnesium and argon, are calculated in the framework of relativistic multiconfiguration Dirac-Fock method. Convergence of the correlation energies is studied as the active set of orbitals is increased. The Breit interaction is treated fully self-consistently. The final results can be used in the accurately determination of atomic masses from highly charged ions data obtained in Penning-trap experiments.

Journal of Quantitative Spectroscopy and Radiative Transfer, 174 + (2016) 79-87. doi:10.1016/j.jqsrt.2016.01.026

Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

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.

The C 1s and N 1s photoelectron spectra of gas-phase 5-aminotetrazole (5ATZ) were recorded using synchrotron radiation, with the aim of evaluating 1H/2H tautomer population ratios. The core-electron binding energies (CEBEs) were estimated from computational results, using the delta self-consistent-field (ΔSCF) approach. Simulated spectra were generated using these CEBEs and the results from Gaussian-n (Gn, n=1, 2 and 3) and Complete Basis Set (CBS-4M and CBS-Q) methods. Results reveal the almost exclusive predominance of the 2H-tautomer, with a 1H/2H ratio of ca. 0.12/0.88, taken from a gross analysis of the XPS C 1s spectrum, recorded at 365 K.

The C 1s and N 1s photoelectron spectra of gas-phase 5-aminotetrazole (5ATZ) were recorded using synchrotron radiation, with the aim of evaluating 1H/2H tautomer population ratios. The core-electron binding energies (CEBEs) were estimated from computational results, using the delta self-consistent-field (ΔSCF) approach. Simulated spectra were generated using these CEBEs and the results from Gaussian-n (Gn, n=1, 2 and 3) and Complete Basis Set (CBS-4M and CBS-Q) methods. Results reveal the almost exclusive predominance of the 2H-tautomer, with a 1H/2H ratio of ca. 0.12/0.88, taken from a gross analysis of the XPS C 1s spectrum, recorded at 365 K.

The relative populations of the 1H- and 2H-tautomer of gas-phase 5-methyltetrazole (5MTZ) have been assessed through core-level photoelectron spectroscopy, and compared with the results obtained from Gaussian-n (Gn, n = 1, 2 and 3) and Complete Basis Set methods (CBS-4M and CBS-Q). The C 1s and N 1s core‚Äìelectron binding energies (CEBEs) for each ionization site of both tautomers have been computed using the Œîself-consistent-field (ŒîSCF) approach. The C 1s and N 1s XPS spectra, obtained at 313 K, yield a 1H/2H tautomer ratio of ca. 0.16/0.84 and 0.21/0.79, respectively.

Chemical Physics Letters, 516 (2011) 149-153. doi:10.1016/j.cplett.2011.10.001

The relative populations of the 1H- and 2H-tautomer of gas-phase 5-methyltetrazole (5MTZ) have been assessed through core-level photoelectron spectroscopy, and compared with the results obtained from Gaussian-n (Gn, n = 1, 2 and 3) and Complete Basis Set methods (CBS-4M and CBS-Q). The C 1s and N 1s core‚Äìelectron binding energies (CEBEs) for each ionization site of both tautomers have been computed using the Œîself-consistent-field (ŒîSCF) approach. The C 1s and N 1s XPS spectra, obtained at 313 K, yield a 1H/2H tautomer ratio of ca. 0.16/0.84 and 0.21/0.79, respectively.

n/a

An extensive conformational analysis was carried at ab initio and DFT levels of theory on two molecules - methyl 2-azidopropionate (N3CH3CHCOOCH3) and methyl 3-azidopropionate (N3CH2CH2COOCH3). In each case, the lowest energy conformers were characterized and the energy barriers between them were estimated. Ionization energies and vibrational frequencies were also computed, in order to support future spectroscopic studies with ultraviolet photoelectron spectroscopy (UVPES) and matrix isolation infrared spectroscopy (Matrix Isolation FTIR).

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.

n/a