Core ionization potentials in dimethyl ether and methyl amine

The ionization potentials for core electrons in dimethyl ether and methyl amine have been measured. For carbon 1s electrons the values are 292.25(4) eV for the ether and 291.60(4) eV for the amine. The nitrogen 1s ionization potential is 405.15(4) eV; that for oxygen is 538.59(4) eV. The two ionization potentials for the ether are very close to those that have been reported for the related compound methanol. Those for methyl amine reflect the fact that nitrogen is more electro-negative than carbon. The carbon 1s ionization potential in methyl amine together with the equivalent cores approximation gives an estimate of 169 kcal/mole for the heat of formation of N₂H₅⁺. The corresponding proton affinity for hydrazine is 221 kcal/mole, very close to that of ammonia, 214 kcal/mole. The large shifts of nitrogen and oxygen core ionization potentials relative to N₂ and O₂ may be due to unusually low relaxation energies for the diatomic molecules rather than to high negative charges on the atoms in the respective compounds. Since different methods for estimating relaxation energies give results differing by as much as 6 eV, it is not possible to say which is the more important effect.     

Core ionization potentials in carbon monoxide

Conflicting values have been reported for the core ionization potentials in carbon monoxide. We have remeasured these and find 296.24 ± 0.03 for the carbon 1s ionization potential and 542.57 ? 0.03 for oxygen 1s. The carbon value is close to previously reported values; that for oxygen is higher by ～ 0.5 eV. These results are compared with ionization potentials calculated from molecular orbital theory. The value predicted by near-Hartree-Fock calculations for oxygen is too low by ～ 1eV and that for carbon is too high by ～ 0.5 eV.     

UV photoelectron spectra and sum rule consideration: Out-of-plane orbitals of unsaturated compounds with planar-skeleton structure

He(l) photoelectron spectra are presented for various planar unsaturated aliphatic compounds such as mono- and di-methyl substituted ethylenes, alkyl aldehydes, chloro-substituted aldehydes, ketones and alkyl acids. Each photoelectron spectrum is resolved into individual bands by considering the band shape, the relative intensity and the number of p-type localized MO's (LO's). The sum rule previously proposed on vertical ionization energies by the present authors is applied to the photoelectron bands associated with out-of-plane LO's. In each compound, a partial sum P(a″) is obtained over all the out-of-plane LO's and it is shown that the calculated P(a″) value is in good agreement with the experimental one which may be obtained by an appropriate sum of vertical ionization energies with negative signs.     

Multi-reference configuration-interaction calculations on multiply charged ions of carbon monosulfide

The potential energy curves for neutrals and multiply charged ions of carbon monosulfide are computed with highly correlated multi-reference configuration interaction wavefunctions.The correlations of inner-shell electrons with the scalar relativistic effects are included in the present computations.The spectroscopic constants,dissociation energies,ionization energies for ground and low-lying excited states together with corresponding electronic configurations of ions are obtained,and a good agreement between the present work and existing experiments is found.No theoretical evidence is found for the adiabatically stable CSq+(q>2) ions according to the present ab initio calculations.The calculated values for 1st-6th ionization energies are 11.25,32.66,64.82,106.25,159.75,and 224.64 eV,respectively.The kinetic energy release data of fragments are provided by the present work for further experimental comparisons.     

Laser Ionization Spectroscopy of Octafluorocyclooctatetraene

Two- and three-photon resonant ionization spectroscopy is used to explore the high-lying electronic states of octafluorocyclooctatetraene (OFCOT). CNDO/S calculations are reported as an aid in the assignment of the observed valence transitions. The spectra agree quite well with the predictions of the semi-empirical method, which has not been previously tested at such high energies. The ionization potential for this molecule is estimated and the effects of “through-space” and “through-bond” coupling on the energy levels are discussed. Comparison is made to the already reported spectroscopy of the hydrocarbon analog.     

Inner-shell ionization of atoms by electron,positron and photon impacts

Plane wave Born approximation with Coulomb, relativistic and exchange corrections is employed to obtain L1-, L2- and L3-subshell ionization cross sections of several atoms due to electron and positron impacts for projectile energy varying from the threshold of ionization to 60 times the threshold energy. Photoionization cross sections for all the three L-subshells of the atoms are also calculated using the hydrogenic approximation for the atomic wave functions. For L3-subshell the present cross sections due to electron impact are in good agreement with a number of experimental data for different atoms over the entire energy range investigated. For L1- and L2-subshells the present calculations yield qualitative agreement with the experimental data. The agreement between the present results and the limited experimental data for positron impact is also satisfactory. The hydrogenic approximation for the L-subshell photoionization is found to be good at small photon energies but it underestimates the cross sections at large photon energies.     

An ESCA study of organosilicon compounds

The silicon 2p electron binding energies have been measured for a series of 33 organosilicon compounds. The binding energies are correlated with partial atomic charges calculated by various electronegativity models and CNDO calculations. Group shifts are reported for various chemical groups attached to silicon and are found to correlate with group shifts reported for carbon and phosphorus compounds.     

Relativistic calculations of electron-impact ionization for highly charged hydrogen-like ions

Electron-impact ionization cross-sections and rate coefficients of the 1s ground state for H-like C, O, Mg, Ar, Fe, Cu, As, Kr, Y, Mo ions with incident electron energies up to 15 times the ionization threshold energy have been systematically calculated by the relativistic distorted-wave Born exchange (DWBE) approximation. The comparison of the result with the experimental data, other theoretical calculations and recommended values shows the very good agreement. The influence from relativistic and the lowest order QED effect in the calculation is discussed. The calculated ionization cross-sections are fitted by empirical formulas. These fits can be readily integrated over a relativistic Maxwellian electron distribution function to obtain rate coefficient for plasma modeling.     

Theoretical study on 2s2p6np Rydberg states of Cu19+ ion

We report on the calculations of transition wavelengths and weighted oscillator strengths for 2s²2p⁶-2s2p⁶ⁿp (4 ≤ n ≤ 20) electric dipole (E1) transitions of Cu¹⁹⁺ ion. The flexible atomic code (FAC) has been adopted for the calculations. Comparisons are made with the experimental data available, showing that the present results for 4 ≤ n ≤ 6 are more accurate than the previous calculated values. Furthermore, combining the quantum defect theory (QDT) with the transition energies of 2s²2p⁶-2s2p⁶np, the quantum defects for 2s2p⁶np Rydberg series of Cu¹⁹⁺ ion are determined. In addition, the energies of any highly excited states (n > 20) for this series can be reliably predicted using the QDT and the given quantum defects. The ionization energies for Cu¹⁹⁺ and Cu²⁰⁺ ions are also calculated and they excellently accord with previous experimental and calculated values.     

Semi-empirical calculation of air-broadened half-widths and air pressure-induced frequency shifts of water-vapor absorption lines

This paper describes a semi-empirical calculation of the air-broadened half-widths and the air pressure-induced frequency shifts for the H₂¹⁶O isotopologue. This semi-empirical calculation is based on fits of several recent high-quality measurements and theoretical calculations to the first-order terms in the expansion of the complex Robert-Bonamy (CRB) equations, which yields a second- and first-order polynomial function of the differences in the upper- and lower-state vibrational quantum numbers for the half-width and line shift, respectively. The aim of this work was to obtain a complete set of air-broadened half-widths and air pressure-induced frequency shifts for transitions of H₂¹⁶O present in the HITRAN database from microwave to the visible in order to supplement the observed and calculated values. For around 700 sets of rotational quantum numbers (), semi-empirical coefficients describing the vibrational dependence of the air-broadened half-widths and the air pressure-induced frequency shifts have been obtained directly from the fit of experimental and/or theoretical data. The accuracy of the parameters deduced from this calculation is estimated to be between 5% and 10% for the air-broadened half-widths and between 0.001 and for the air pressure-induced frequency shifts. For sets of rotational quantum numbers for which either none or insufficient experimental/theoretical data were available to deduce a vibrational dependence, further approximations have been used to obtain a complete set of semi-empirical coefficients.     

Correlation between core level chemical shifts obtained by ultrasoft x-ray emission and ESCA

High resolution C:K X-ray emission spectra have been recorded from six molecules in the gas phase. The spectra are interpreted by comparing the relative X-ray energies with the vertical ionization energies of the valence orbitals and comparing the intensities predicted by the C 2p populations from CNDO calculations with the measured intensities. The obtained C 1s binding energy shifts are found to be in excellent agreement with shifts measured with ESCA.     

Correlation between core level chemical shifts obtained by ultrasoft X-ray emission and ESCA

High resolution C:K X-ray emission spectra have been recorded from six molecules in the gas phase. The spectra are interpreted by comparing the relative X-ray energies with the vertical ionization energies of the valence orbitals and comparing the intensities predicted by the C 2p populations from CNDO calculations with the measured intensities. The obtained C 1s binding energy shifts are found to be in excellent agreement with shifts measured with ESCA.     

Electron inelastic interactions in bioorganic compounds in the energy range of 20–10000 eV

Systematic calculations of stopping powers (SPs) and mean free paths (MFPs) for 10 bioorganic compounds have been performed for electrons with energies lower than 10 keV, based on dielectric response theory and Penn’s statistical approximation. The exchange effect is also taken into account in the calculations. An empirical approach to obtain an optical energy loss function is presented for those organic compounds without available optical data. Using this method, the calculated values of the optical energy loss function are in good agreement with experimental data. Comparisons of SP and MFP values derived in this study with other published values are presented. Using the described model, the calculated mean ionization potentials agree well with the predictions from Bragg’s rule and the calculated SPs have also been compared with the Bethe–Bloch results at an energy of 10 keV. PACS 34.50.Bw; 61.82.Pv     

Long range interactions of the Mg+ and Ca+ ions

The polarizabilities of the low lying states of the Mg⁺ and Ca⁺ ions are evaluated by diagonalizing the semi-empirical Hamiltonians in a large dimension single electron basis. The quadrupole moment of the metastable 3d state Ca⁺ is also calculated and is within 1% of a recent experimental value while being 5% smaller than some large ab-initio calculations. In addition, the long range dispersion coefficients for these ions interacting with a number of atoms are given. Oscillator strengths are also given and generally agree with the most sophisticated ab-initio calculations. The polarizabilities and dispersion coefficients can be used to estimate the frequency shifts of the Ca⁺ 4s ↦ 3d clock transition due to background electric fields and also collisions with a buffer gas.     

A CNDO/2 study of σ- and π- relaxation energies and core electron binding energy shifts in some simple molecules

A relaxation potential model has been used to study relaxation energies and shifts in core electron binding energies for some substituted alkenes and carbonyl compounds in terms of σ- and π-contributions.The conclusions from this study may be summarized as follows:(A) For the series R₁R₂C^*CH₂ and R₁R₂C^*O: (i) The total shifts vary in a regular manner, similar to the shifts in saturated systems; (ii) The variation in σ-relaxation energies is greater than the variation in π-relaxation energies.(B) For the series R₁R₂CCH₂ and R₁R₂CO: (i) There is little variation in the σ-relaxation energies; (ii) The π-relaxation energies show moderately large variations and the higher values are associated with unsaturated substituents which can donate π-electrons to the core-ionized atom via the conjugated π-system; (iii) The π-relaxation energies in the fluorinated systems are similar to those in the unsubstituted molecules; and (iv) The large -ve π-shift in the fluorinated systems results from a ground state build up of electron density at the site of core ionization.     

Electron impact ionization cross sections of beryllium and beryllium hydrides

We report calculated electron impact ionization cross sections (EICSs) for beryllium (Be) and some of its hydrides from the ionization threshold to 1 keV using the Deutsch-Märk (DM) and the Binary-Encounter-Bethe (BEB) formalisms. The positions of the maxima of the DM and BEB cross sections are very close in each case while the DM cross section values at the maxima are consistently higher. Our calculations for Be are in qualitative agreement with results from earlier calculations (convergent close-coupling, R matrix, distorted-wave and plane-wave Born approximation) in the low energy region. For the various beryllium hydrides, we know of no other available data. The maximum cross section values for the various compounds range from 4.0 × 10^?16 to 9.4 × 10^?16 cm² at energies of 44 to 56 eV for the DM cross sections and 3.0 × 10^?16 to 5.4 × 10^?16 cm² at energies of 40.5 to 60 eV for the BEB cross sections.     

Limitation of semi-empirical mo-calculations in deriving charge densities ρ(0) in iron-oxygen compounds

For fifteen iron-oxygen compounds we carry out semi-empirical MO cluster calculations. The derived electronic structure is used to calculate electron charge densities ρ(0) and electric field gradients V_pq at the iron nucleus. The ρ(0)-values correlate with experimental isomer shifts δ, however, extreme cases like the Fe(VI)-compound BaFeO₄ are beyond the scope of accuracy of our method. We discuss variations of our calculational method, with one of them leading to ρ(0)-values for all fifteen compounds (including BaFeO₄) which satisfy the relation Δδ = αΔρ(0). The isomer shift calibration constant is in the range -0.195 mms^?1a₀³ to -0.25 mms^?1a₀³. Calculated quadrupole splittings are comparable with experimental data.     

The total charge-changing cross sections and the partial cross sections of 56Fe fragmentation on Al,C and CH2 targets

The total charge-changing cross sections and the partial cross sections of ⁵⁶Fe fragmentation on polyethylene, carbon and aluminum targets at the highest energy of 496 A MeV are investigated using CR-39 plastic nuclear track detector. The total charge-changing cross-section for hydrogen target is calculated based on the results of polyethylene and carbon targets. It is found that the total charge-changing cross sections for fragmentation of ⁵⁶Fe on hydrogen, carbon and aluminum targets are independent on the beam energy in our studied energies, and are consistent with the predictions of Bradt–Peter semi-empirical formula, Nilsen parameterized formula, NUCFRG2 and QMSFRG theoretical simulation codes. The partial cross sections for projectile fragment production are independent on beam energy in our studied energies for each targets and do not show a significant even-odd effect.     

The catalytic activity of chemisorbed oxygen and carbon monoxide species on palladium and related metals investigated using SCF-Xα-SW calculations

Theoretical calculations of the electronic structure of small clusters modelling the adsorption of carbon monoxide on nickel and palladium and the adsorption of oxygen on palladium and platinum have been carried out using the SCF-Xα-SW method. Our results for the carbon monoxide-nickel clusters are in good agreement with earlier work. Comparing the carbon monoxide-nickel with the carbon monoxide-palladium results, suggests that the ordering of CO-derived cluster orbitals is the same in both cases but that the relative shifts are much different. In addition, the oxygen atom participates more significantly in the cluster containing palladium. An analysis of optical transition energies for Ni₅CO and Pd₅CO clusters is given and discussed in terms of experimental data regarding photodesorption of carbon monoxide. In the case of oxygen atoms in platinum and palldium clusters, we have used two different M₅O geometries: one in which the five metal atoms are in a single plane and oxygen is directly over a single metal atom (Type A) and a second in which the oxygen atom is coordinated to four sur face metal atoms and is directly over a metal atom in the second layer (Type B). The levels calculated for the Pd50 type B cluster are in good agreement with available UPS data. Significant differences in type A and type B clusters are noted for palladium. The results can be correlated with experimental Auger spectroscopic and kinetic data. In particular, the type A oxygen cor relates well with an experimentally observed very reactive species, while type B oxygen cor relates well with a quite unreactive species. These two types also correlate with two species observed by Auger spectroscopy.