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Chemical bonding is taken into account explicitly in the determination of the mean excitation energy (I) for stopping power of H2 with the local plasma approximation by employing molecular electronic wave functions for H2 for the first time. This procedure leads to a new value for IH2 that is higher than all accepted experimental and theoretical values.
The interaction of CO with Cu5, Ni5, and Al4 are treated as model systems for molecular adsorption on metal surfaces. The effect of the use of pseudopotentials for the metal atoms is studied by considering three types of clusters. In the first case, all of the metal electrons are explicitly included in the wave function; an all electron (AE) treatment. In the second case, the metal atom which directly interacts with the CO is described by AE but the remaining metal atoms include a pseudopotential for their core electrons. Finally, in the third case, all of the metal atoms in the cluster have a pseudopotential treatment for the core electrons. The AE cluster results are taken as reference values for the two pseudopotential treatments. The mixed cluster results are in excellent agreement with those of the all AE clusters; however, the results for the all pseudopotential cluster of Ni5CO or of Cu5CO are qualitatively different. The pseudopotential treatment for all of the metal atoms often leads to results that contain serious errors and it is not a reliable approach.
The p(2 x 2) and c(2 x 2) coverages of S on Ni(100) are studied with a cluster model. Consistent with a recent lattice-dynamics study, the chemical contribution (rigid Ni lattice) to the coverage-dependent shift of the S vibrational energy is of opposite sign to that for O. Analysis of the cluster wave functions suggests that S becomes less negatively charged with coverage, while O becomes more ionic; however, this effect is small.
It is shown that the relative intensity distribution among the X-ray spectral lines of helium-like ions from the n = 2 states produced through recombination processes such as radiative and charge transfer recombination may be given by considering in detail the radiative cascades following recombination. Model calculations are presented with predicted line ratios for Ar XVII and Fe XXV in recombination-dominated noncoronal plasmas. In particular, compared to coronal intensities, the singlet resonance line (w) should be much weaker relative to the triplet intercombination (x, y) and forbidden (z) lines, yielding large values for the ratio G = (x + y + z)/w. Accurate configuration interaction type wave functions are employed to calculate the eigenenergies, transition probabilities, and cascade coefficients. Certain relevant tokamak and astrophysical observations are discussed.
It is known that very strong (greater than 1-TG) magnetic fields exist on the surface of some neutron stars. The properties of atoms in fields of this nature are considerably different from those of atoms in field-free regions. Because of the mixing of spherical and cylindrical symmetries, the analytical solution to the problem of a hydrogen atom in a uniform magnetic field is impossible to obtain. In this work, a variational wave function is used to describe the properties of hydrogen like atoms in intense magnetic fields including first-order relativistic effects. Special attention is given to the transition matrix elements for the 2p(0) - 1s(0) transition in Fe XXVI.
Oscillator strengths between various doublet states of OII ions are calculated in which extensive multi-configuration wave functions are used. The lower levels for the transitions are of the 2p(3) D(2)o and 2p(3) 2po states, and the upper levels are 2p(4), 3s, and 3d states. The results, which are estimated to have errors of less than 10 percent for individual transitions, agree quite well with the beam foil experiments, as well as with the calculations by use of the non-closed shell many-electron theory (NCMET). The agreement with the rocket measurements is also good except for the 538/581 A pair, in which the 538 A line is believed to blend with the other stronger quartet line. However, a comparison with the recent branching ratio measurement indicates that discrepancies between the present calculation and the experiment do exist for certain transitions.
A large optical Stark effect has been observed in the two-photon spectrum X(2)Pi yields A(2)Sigma(+) - in NO. It is explained as a near-resonant process in which the upper state of the two-photon transition is perturbed by interactions with higher-lying electronic states coupled by the laser field. A theoretical analysis is presented along with coupling parameters determined from ab initio wave functions. The synthetic spectrum reproduces the major experimental features.
An optimal frequency domain textural edge detection filter is developed and its performance evaluated. For the given model and filter bandwidth, the filter maximizes the amount of output image energy placed within a specified resolution interval centered on the textural edge. Filter derivation is based on relating textural edge detection to tonal edge detection via the complex low-pass equivalent representation of narrowband bandpass signals and systems. The filter is specified in terms of the prolate spheroidal wave functions translated in frequency. Performance is evaluated using the asymptotic approximation version of the filter. This evaluation demonstrates satisfactory filter performance for ideal and nonideal textures. In addition, the filter can be adjusted to detect textural edges in noisy images at the expense of edge resolution.
Ab initio quantum chemical techniques are used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types are identified. Basis sets of polarized double zeta quality and large scale configuration interaction wave functions are utilized. Based on electronic energies, the covalently bonded HOOOH species is 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen bonded HO---HO2 species has an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen bonded form is planar, possesses one relatively normal hydrogen bond, and has the lowest energy 3A' and 1A' states that are essentially degenerate. The 1A" and 3A" excited states produced by rotation of the unpaired OH electron into the molecular plane are very slightly bound.
Recent studies into the nature of bonding at the interface between two solids in contact or a solid and deposited film have provided a better understanding of those properties important to the adhesive wear resistance of materials. Analytical and experimental progress are reviewed. For simple metal systems the adhesive bond forces are related to electronic wave function overlap. With metals in contact with nonmetals, molecular-orbital energy, and density of states, respectively can provide insight into adhesion and wear. Experimental results are presented which correlate adhesive forces measured between solids and the electronic surface structures. Orientation, surface reconstruction, surface segregation, adsorption are all shown to influence adhesive interfacial strength. The interrelationship between adhesion and the wear of the various materials as well as the life of coatings applied to substrates are discussed. Metallic systems addressed include simple metals and alloys and these materials in contact with themselves, both oxide and nonoxide ceramics, diamond, polymers, and inorganic coating compounds, h as diamondlike carbon.
Self consistent field and correlated wave functions have been computed for the ground and for several low-lying states of CuO. The ground state is X(2)PI and the lowest excited state, at approximately 8,000/cm above X(2)PI, is a previously unidentified 2-sigma(+) state. The separation of these states is compared to that for the similar states of KO and is analysed in terms of integrals between orbitals of the separated free ions. A classification of the states of the molecule based on states of Cu(+) and O(-) which leads to a division into manifolds of states arising from Cu(+) 3d(10) and Cu(+) 3d(9) 4s(1) is considered. It is predicted that the state of the 3d(9) 4s(1) manifold are 10,000 to 30,000/cm above the ground state and assign the observed A2-sigma(+) state at 16,500/cm to this manifold.
Full configuration-interaction calculations are reported, and compared to other methods, for H2O at its equilibrium geometry and at two geometries with the H-O bonds stretched. Since the percentage of the self-consistent field (SCF) reference in the full configuration-interaction (FCI) wave function decreases greatly with the bond elongation, the accuracy of techniques based on a single reference do not compare well with the FCI results. However, the results from a complete active space SCF/multireference configuration-interaction (CASSCF/MRCI) treatment are in good agreement with the FCI. Correlation effects in F compared to Ne are far more similar than for F- compared to Ne, despite F- and Ne being isoelectronic. Since the importance of higher than double excitations is more important for F- than F, a very high percentage of the correlation must be obtained to accurately compute the electron affinity. In a CASSCF/MRCI treatment the higher than quadruple excitations contribute 0.02 eV to the electron affinity (EA), even for modest basis sets.
Full configuration-interaction (FCI) calculations are performed at selected geometries for the 1-sigma(+) state of HF and the 2-B(1) and 2-A(1) states of NH2 using both DZ and DZP gaussian basis sets. Higher excitations become more important when the bonds are stretched and the self-consistent field (SCF) reference becomes a poorer zeroth-order description of the wave function. The complete active space SCF - multireference configuration-interaction (CASSCF-MRCI) procedure gives excellent agreement with the FCI potentials, especially when corrected with a multi-reference analog of the Davidson correction.
The electron affinity (EA) of oxygen is computed to be 1.287 eV, using 2p electron full configuration-interaction (CI) wave functions expanded in a 6s5p3d2f Slater-type orbital basis. The best complete active space self-consistent field - multireference CI (CASSCF-MRCI) result including only 2p correlation is 1.263 eV. However, inclusion of 2s intrashell and 2s2p intershell correlation increases the computed EA to 1.290 at the CASSCF-MRCI level. At the full CI basis set limit, the 2s contribution to the electron affinity is estimated to be as large as 0.1 eV. This study clearly establishes the synergistic effect between the higher excitations and basis set completeness on the electron affinity when the 2s electrons are correlated.
A calculated dipole moment of 2.39 D at R sub e = 2.79 a sub 0 is reported, obtained from complete active space SCF/configuration interaction calculations plus one natural orbital iteration. The calculation is in good agreement with the experimental value of 2.4 + or - 0.1 D measured for the lowest vibrational level. In agreement with Gray et al. (1985), it is found that the dipole moment is strongly correlated with the 3d electron population; the good agreement with experiment thus provides verification of the mixed state model of NiH. It is concluded that the electric dipole moment of NiH is a sensitive test of the quality of the NiH wave function.
The present paper is concerned with an analysis of the bonding in Fe2(CO)9, taking into account the results of self-consistent-field (SCF) calculations. The basis sets used are the same as those employed in the study of Fe(CO)5 conducted by Bauschlicher and Bagus (1985). The Fe basis set starts with the 14s9p5d primitive set optimized by Wachters (1970), which is contracted to 8s4p5d. An SCF wave function, consisting of only the core electrons, was determined, and then electrons were slowly added to the virtual orbitals with the lowest eigenvalues. The conducted calculations show no direct Fe-Fe bonding, but rather bonding resulting from the bridging CO's. The bonding is found to involve both the 5 sigma and 2 pi(asterisk) orbitals of the bridging CO's.
Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.
Ab initio quantum chemical techniques have been used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types were identified. Basic sets of polarized double-zeta quality and large scale configuration interaction wave functions have been utilized. Based upon electronic energies, the covalently-bonded HOOOH species is found to be 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen-bonded HO-HO2 species is found to have an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen-bonded form is found to be planar, to possess one relatively 'normal' hydrogen bond, and to have lowest energy 3A-prime and 1A-prime states that are essentially degenerate. The 1A-double prime and 3A-double prime excited states produced by rotation of the unpaired OH electron into the molecular plane are found to be very slightly bound.