Symmetry and equivalence restrictions in electronic structure calculations

A simple method for obtaining MCSCF orbitals and CI natural orbitals adapted to degenerate point groups, with full symmetry and equivalnece restrictions, is described. Among several advantages accruing from this method are the ability to perform atomic SCF calculations on states for which the SCF energy expression cannot be written in terms of Coulomb and exchange integrals over real orbitals, and the generation of symmetry-adapted atomic natural orbitals for use in a recently proposed method for basis set contraction

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2

On the electron affinities of the Ca, Sc, Ti and Y atoms

For the Ca, Sc, Ti and Y atoms calculations are performed for the ground states of the neutrals and the ground and several low-lying excited states of the negative ions. Overall the computed electron affinities are in good accord with experiment. The calculations show the rapid stabilization of the 3d orbital relative to the 4p as the nuclear charge increases. The 3F(0) and 3D(0) terms are found to be close in energy in Sc(-) and in Y(-). This confirms earlier speculation that some of the peaks in the photodetachment spectra of Y(-) originate from the bound excited 3F(0) term of Y(-)

Accurate quantum chemical calculations

An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed

Theoretical study of the dissociation energy and the red and violet band systems of CN

The dissociation energy (D sub O) of CN is determined to be 7.65 + or - 0.06 eV. This corresponds to delta H sub f (CN) = 105.3 + or - 1.5 kcal/mole, in excellent agreement with Engleman and Rouse (1975), but considerably larger than the recent value deduced from shock-tube studies by Colket (1984). The result is obtained not only from extensive ab initio MRCI calculations using a very large Gaussian basis set, but also from extrapolation of the directly computed value by comparison of computed and experimental results fo NO, C2, and N2. As an additional calibration of the methods, the D sub O value for CN was computed from the corresponding value for CN(-) using the experimental electron affinity data. The lifetime of the nu prime = 0 level of the violet (B 2 sigma + yields X 2 sigma +) system was computed to be 62.4 ns, in good agreement with both experiment and previous calculations. Lifetimes for the red (A 2 pi yields X 2 sigma +) system decrease with increasing nu prime, which is consistent both with the recent experiment and calculations. While the computed lifetimes are significantly longer that those obtained from the experiment, they are shorter than those deduced from an analysis of the solar spectrum. However the D sub O and f (sub OO) are consistent with Lambert's model for the solar spectrum

Theoretical study of the C-H bond dissociation energy of acetylene

The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound

The 2D Rydberg series in Al I

High quality ab initio electonic structure calculations were performed on the 2D Rydberg series in Al I. The configuration 3s3p2(2D) is shown to contribute substantially to the lowest four 2D Rydberg states. The same configuration also contributes substantially to a 2D state embedded in the ionization continuum. Computed oscillator strengths for the first six members of the 2D Rydberg transitions are given: these should be of substantially high accuracy than currently available values

Core-core and core-valence correlation

The effect of (1s) core correlation on properties and energy separations was analyzed using full configuration-interaction (FCI) calculations. The Be 1 S - 1 P, the C 3 P - 5 S and CH+ 1 Sigma + or - 1 Pi separations, and CH+ spectroscopic constants, dipole moment and 1 Sigma + - 1 Pi transition dipole moment were studied. The results of the FCI calculations are compared to those obtained using approximate methods. In addition, the generation of atomic natural orbital (ANO) basis sets, as a method for contracting a primitive basis set for both valence and core correlation, is discussed. When both core-core and core-valence correlation are included in the calculation, no suitable truncated CI approach consistently reproduces the FCI, and contraction of the basis set is very difficult. If the (nearly constant) core-core correlation is eliminated, and only the core-valence correlation is included, CASSCF/MRCI approached reproduce the FCI results and basis set contraction is significantly easier

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations

Report from space plasma science

Space plasma science, especially plasma experiments in space, is discussed. Computational simulations, wave generation and propagation, wave-particle interactions, charged particle acceleration, particle-particle interactions, radiation transport in dense plasmas, macroscopic plasma flow, plasma-magnetic field interactions, plasma-surface interactions, prospects for near-term plasma science experiments in space and three-dimensional plasma experiments are among the topics discussed