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  • 1970-1974  (363)
  • 1973  (363)
  • Engineering  (189)
  • Computational Chemistry and Molecular Modeling  (108)
  • Rat  (66)
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  • 1970-1974  (363)
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  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 63-73 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The exchange polarization energy and higher-order exchange corrections arising in the second order of the Murrell-Shaw and Musher-Amos (MS-MA) theory are evaluated analytically for the hydrogen molecule ion. At large internuclear distances the second-order exchange energy predicted by MS-MA theory behaves like \documentclass{article}\pagestyle{empty}\begin{document}$- \frac{1}{{18}}Re^{ - R}$\end{document}. It represents only 80% of the difference between the exact result of Holstein and the asymptotic value of the first-order exchange energy. The same result holds for the case of Hirschfelder-van der Avoird (HAV) and Hirschfelder-Silbey (HS) theories.
    Additional Material: 3 Tab.
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  • 102
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 127-130 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 103
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 569-581 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Applying an extended form of the Mulliken approximation and a monopole approximation for the Coulomb integrals the Hartree-Fock nonorthogonal energy expression is decoupled. Thus, the total energy splits into a sum of one-electron increments. The increments are minimized directly with respect to the linear coefficients and orbital exponents. Further, the ZDO approximation is used in the decoupled energy expression to avoid difficulties arising in connection with the evaluation of multicenter integrals. “Rigid core” calculations were carried out for the valence electrons of first-row diatomics. In case of nonpolar molecules good results are obtained for equilibrium distances and force constants. The method fails for molecules with atoms having very different nuclear charges.
    Additional Material: 1 Ill.
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  • 104
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 609-622 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various molecular properties have been calculated for pyridine and pyrazine from Gaussian lobe ab initio SCF molecular wave functions. Values are compared with available experimental data. In general, agreement is satisfactory with the exception of the rather sensitive asymmetry parameter of the quadrupole coupling tensor. The distributions of total electronic charge, and of selected molecular orbitals have been displayed as plots of the charge density contours in two dimensions.
    Additional Material: 8 Ill.
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  • 105
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 641-646 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For an estimation of the pair correlation the interelectronic distance r12 in geminal ψk(12) is introduced. The calculations are carried out by the local energy method [1, 2]. The influence of other electrons are taken into consideration with the help of the one- and two-electron integrals depending upon r1 and r2 as parameters. If the strong orthogonality condition is satisfied all two-electron integrals and most of the one-electron integrals vanish. All atomic orbitals are expressed in terms of Gaussian functions. A trial calculation is made for the beryllium atom.POUR tenir compte de la corrélation, on introduit la distance interélectronique r12 dans la géminale ψk(12). Le calcul est réalisé par une méthode des énergies locales [1, 2]. L'influence des autres électrons est décrite par des intégrales à un et deux electrons, dépendantes de r1 et r2 comme paramètres. Dans les conditions de l'orthogonalité forte, toutes les intégrales à un électron et la plupart des intégrales à deux électrons disparaissent. Pour simplifier l'algorithme du problème, toutes les orbitales sont exprimées par les fonctions de Gauss. Le calcul est réalisé sur le modèle de l'atome Be.Für Berechnung der Korrelation wird der Interelektronenabstand r12 in Geminal ψk(12) eingeführt. Die Berechnung wird mit der Lokalenenergiemethode durchgeführt [1, 2]. Die Einwirkung der anderen Elektronen wird durch 1- und 2-Elektronenintegrale berücksichtigt, die von Parametern r1 und r2 abhängen. Bei Erfüllung der starken Orthogonalitätsbedingung verschwinden alle 2-Elektronen- und die Mehrzahl der 1-Elektronenintegrale. Alle Orbitale werden durch Gaussfunktionen ausgedrückt. Eine Berechnung für das Atom Be wird durchgeführt.
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  • 106
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 675-686 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As until now proposed in the literature, in the local energy calculations we can distinguish “few-points” procedures, in which the number M of configurational points is strictly related to the number N of trial functions used, and statistical “many-points” procedures, in which the number M of points can be arbitrarily increased. In this paper we demonstrate that the energy errors resulting from a “many-points” calculation M points/N functions (M 〉 N) can be connected in a simple way with the errors of the (MN) partial calculations N points/N functions.This suggests a possible approach for the problem of the choice of the configurational points to be introduced in the calculation, and leads to a simple interpretation of the numerical meaning of the error associated with the ordinary Ritz energy. Numerical examples on the hydrogen atom are reported.
    Additional Material: 1 Ill.
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  • 107
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    International Journal of Quantum Chemistry 7 (1973), S. 717-723 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown how to obtain pseudonatural orbitals directly from the equations of motion. A sample calculation on the ground state of the Be atom is given.
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  • 108
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 7 (1973), S. 155-171 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Exchange perturbation theory of the Rayleigh-Schrödinger type is applied, in first and second orders, to the problem of bonding in rare-gas halides. The basic model is that of a four-electron, three-center system with one effective electron replacing the unpaired electrons of a halogen atom, and two spin-paired electrons representing the closed shells of the rare-gas atom. On the basis of exchange perturbation theory, the model verifies a direct parallelism between bonding in rare-gas compounds and the phenomenon of super-exchange in ionic solids with paramagnetic cations. It is found that the observed stability and specific geometric configuration of the xenon and krypton fluorides are readily reproduced by the model. In addition, the model explains why other dihalides cannot exist. The two principal components of the interaction energy are found to be indirect exchange between halogen atoms via the rare-gas atoms (attractive in the stable configurations) and, in compounds with coordination higher than two, simultaneous interactions between three halogen atoms (always repulsive). The observed approximate constancy of the binding energy per bond in xenon fluorides with increasing coordination is accounted for.
    Additional Material: 4 Ill.
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  • 109
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Slater orbital r12-1 integrals are calculated with a numerical Fourier-transform method based on a formulation first given by Bonham, Peacher and Cox. Spherical wave expansions are introduced that decouple the Feynman integrations for the charge distribution Fourier transforms. The Feynman integrals are evaluated semianalytically, and their properties are analyzed in detail. The final computational step involves a numerical integration over charge distribution quantities. Results for (coplanar) multicenter exchange integrals over 1s orbitals are given. As long as the charge distributions are overlapping considerably, the method gives good results, even when these distributions are highly asymmetric. The method as presently implemented fails when highly disconnected charge distributions are involved.
    Additional Material: 4 Tab.
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  • 110
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    International Journal of Quantum Chemistry 7 (1973), S. 253-284 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tensorial sets adapted to sequences of finite subgroups are applied to the crystal field problem, and a general method for generating sequence-adapted molecular tensors using finite group algebra is formulated. All subgroup sequences of the abstract finite group G(24), isomorphic to the octahedral, O, tetrahedral, Td, and symmetric, S(4), groups are tabulated with explicit isomorphisms provided. The sequences fall into eight equivalence classes. A catalog of irreducible representations of G(24) adapted to a member of each of the eight sequence classes is given together with the transformations which generate representations adapted to all other sequences. With this data it is possible to systematically generate tensorial sets adapted to any sequence of a realization of G(24). Unitary transformations which adapt conventional forms of first- and second-rank irreducible tensorial sets of the rotation group to the eight sequences of the octahedral group are provided. Forms suitable for use with magnetic fields are included. The problem of a d1 ion in a trigonal crystal field is treated with sequence-adapted molecular tensors, and the utility of different sequences for descent in symmetry is discussed.
    Additional Material: 13 Tab.
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  • 111
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    International Journal of Quantum Chemistry 7 (1973), S. 1051-1061 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coarse structure magnetic theory presented here is a reformulation of conventional magnetic theory which emphasizes the spin-free (i.e., the coulombic) nature of the electron-electron interaction. We show that the magnetic properties of a system for which fine and hyperfine structure can be neglected depend only on the energy spectrum of a spin-free Hamiltonian. As an example, we treat the Heisenberg linear chain.
    Additional Material: 1 Ill.
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  • 112
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    International Journal of Quantum Chemistry 7 (1973), S. 1077-1090 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The infinite interaction range model (IIRM) for ferromagnetic systems is presented in its spin-free formulation. In this formulation the states are labelled by partitions which provide a natural variable for thermodynamic computation. We have extended the calculations of Kittel and Shore by computing to a practical thermodynamic limit (N ∼ 100,000). The heat capacity, magnetic susceptibility and the magnetization of the first two functions exhibit a critical temperature while the magnetization is zero at zero field for all temperatures. Spontaneous magnetization is obtained by linear extrapolation from high field or equivalently by a polarized partition function. Relationships are explored among IIRM, the Heisenberg model and the mean field model. Application to IIRM of the Yang-Lee condition for a phase transition yields a critical temperature identical to that obtained by the direct calculation.
    Additional Material: 5 Ill.
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  • 113
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    International Journal of Quantum Chemistry 7 (1973), S. 1175-1182 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical electronic wave functions, potential curves, and expectation values of some one-electron properties are given for the c3IIu state of the hydrogen molecule. The calculations are carried out by the matrix Hartree-Fock method and use a 2-center basis of Slater-type orbitals. A total energy of -0.7292 a.u. is obtained in the best calculation. Our potential curve is reasonably consistent with that calculated by Browne, but we have examined the region of small internuclear distances (those at and below Re for the ground state) more extensively than any previous calculation. At R ≦ 1.6 a.u. our calculated potential curve is in excellent agreement with experiment.
    Additional Material: 1 Ill.
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  • 114
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    International Journal of Quantum Chemistry 7 (1973), S. 1203-1220 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The expressions for matrix elements of spin-independent operators F and G with the use of Young operators are obtained in the case of arbitrary nonorthogonalized orbital configuration, including both singly and doubly filled orbitals and corresponding to the definite value of total spin. The formulas obtained do not require a preliminary construction of linear combinations of determinants and turn into known Löwdin formulas in the particular case of fully antisymmetric spatial states.
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  • 115
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    International Journal of Quantum Chemistry 7 (1973), S. 1227-1228 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 116
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    International Journal of Quantum Chemistry 7 (1973), S. 637-637 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 117
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    International Journal of Quantum Chemistry 7 (1973), S. 699-705 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A discussion of Hartree damping in closed-shell Hartree-Fock theory is given indicating when the method might force convergence of intrinsically divergent cases. An alternative, but closely related principle, “level shifting” is described, and the advantages of the latter procedure discussed.
    Additional Material: 1 Tab.
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  • 118
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    International Journal of Quantum Chemistry 7 (1973), S. 687-698 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The half-projected Hartree-Fock function (HPHF) for singlet states is defined as a linear combination of two Slater determinants, which contains only spin eigenfunctions with even quantum number. Using a self-consistent procedure based on the generalized Brillouin's theorem, the RHF, HPHF and PHF functions are deduced for the ground states of the Li-, Be, B+, and C2+ systems, in a limited basis set. It is found that the HPHF function yields better energy values than the RHF function, very close to that of the PHF one. The HPHF scheme seems thus to be useful as a substitute for the PHF model, specially in the case of large electronic systems in which the latter method becomes unmanageable.
    Additional Material: 1 Ill.
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  • 119
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for the use of the plethysm operation for classification of the permitted electronic terms of impurity complexes in a crystal is presented. The cases of polyatomic symmetrical complexes are discussed as examples.
    Additional Material: 2 Tab.
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  • 120
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    International Journal of Quantum Chemistry 7 (1973) 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 121
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    International Journal of Quantum Chemistry 7 (1973), S. 561-568 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A quadratically convergent process using a continued fraction method for finding the square root of the overlap matrix used in Löwdin orthogonalization is presented. The continued fraction method is compared to several other methods for finding the square root of a matrix. The method is found to be more efficient than the other methods when high accuracy is desired.
    Additional Material: 1 Tab.
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  • 122
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    International Journal of Quantum Chemistry 7 (1973), S. 635-636 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 123
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    International Journal of Quantum Chemistry 7 (1973) 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 124
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    International Journal of Quantum Chemistry 7 (1973), S. 707-715 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A core model approach to the calculation of deuteron quadrupole coupling constants is investigated using NH3 as an example. First the deuteron quadrupole coupling constant is calculated from a CNDO wave function. This result is subsequently improved by recomputing the N - D bond orbital by means of a variational calculation using the CNDO function to construct a core potential for the bond Hamiltonian. In order to simplify integrations a single-center basis is chosen to represent the variational wave function. A projection operator formalism is used as a computational scheme to maintain orthogonality of the bond orbital to core orbitals. Excellent agreement with experiment is obtained. The procedure is applicable to more complicated molecules.
    Additional Material: 4 Tab.
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  • 125
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    International Journal of Quantum Chemistry 7 (1973), S. 779-783 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-dependent variational principle due to Frenkel is derived from Hamilton's principle using a suitable general expression for the variational wave function. The connections with a recent comment of P. O. Löwdin and P. K. Mukherjee on the same subject are discussed.
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  • 126
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    International Journal of Quantum Chemistry 7 (1973), S. 807-817 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By performing calculations on H2 O similar to the calculations of Dunning and McKoy on C2H4 and HCHO [1a], it is shown that the singlet excited states of the water molecule cannot be adequately represented by an ab initio calculation (no semiempirical elements) using a valence-like basis set (either minimum basis or double zeta) of Slater-type orbitals. The triplets which are the lowest states of their symmetry appear to be described more accurately than the other states, and the lowest four triplet excitation energies are calculated to be 8.1, 8.4, 9.5, and 10.3 eV. The implications for the applicability of simple molecular orbital theory of the type commonly applied are discussed.
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  • 127
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several schemes are discussed for partitioning the second-order reduced density matrix Γ into two parts, Γ0 and Γ′.The Γ0s are based on the independent particle model and the Γ′s are corrections due to electron correlation. The difficulties of choosing a Γ0 that will serve as a suitable reference point for studying electron correlation are discussed.In order to compare alternative partitioning schemes, an atomic wave function for the 1S ground state of the Be atom in the configuration-interaction approximation was selected. A fifty-two configuration wave function was computed and contour graphs were made of the total pair density Γ(1 2) and of the “correlation pair density” Γ′(1 2) for several choices of the reference Γ0.
    Additional Material: 14 Ill.
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  • 128
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    International Journal of Quantum Chemistry 7 (1973), S. 927-944 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An interpretation of degenerate symmetry spaces associated with a given atomic or molecular configuration is presented, and the theory necessary for atomic applications is discussed in detail. Löwdin's symmetric projection operator for spin and orbital angular momentum is applied on a well-defined sequence of Slater determinants. In this way a degenerate LS space is divided into orthogonal invariant subspaces which can be classified according to internal couplings of angular momentum. A procedure is found which permits expression of each of these LS eigenfunctions as the smallest possible number of successively orthogonalized projected Slater determinants. In particular, minimum size Hartree-Fock interacting spaces (important in rapidly convergent correlation energy calculations) are obtained in their most compact form. An optimum partition of degenerate spaces of three and four excited (atomic or molecular) configurations is obtained in general. Interpretations, simplifications, and systematizations in atomic configuration interaction calculations are discussed in light of present results.
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  • 129
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    International Journal of Quantum Chemistry 7 (1973), S. 971-984 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1P and 3P states arising from the configuration (1s)2(2s)(2p) of the Be isoelectronic sequence are investigated. In the single configuration approximation, the energies of the two states are expressed as E0 + K2s2p and E0 - K2s2p, respectively. K2s2p is the exchange integral between the 2s and 2p electrons and E0 is the energy of a model in which K2s2p is deleted. First we calculate the 2s- and 2p-orbitals in this model. Second, by taking account of K2s2p in this model, effects of this term on the 2p-orbitals in the 1,3P states are investigated. In this manner, an explanation is given for the following facts which are obtained from a minimal Slater-type orbital set; (1) for Be and B+, the 2p-orbital of the 1P state is broader than that of the 3P state; (2) for C2+, the extension of the 2p-orbital in the two states is almost the same; (3) for O4+ and Ne6+, in contrast to Be and B+, the 2p-orbital of the 1P state is tighter than that of the 3P state.
    Additional Material: 6 Ill.
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  • 130
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    International Journal of Quantum Chemistry 7 (1973), S. 999-1019 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron spin dipole-dipole contribution to the zero field splitting has been evaluated for the 3A2 (n → π*) and 3A1 (π → π*) states of formaldehyde using a CI wave function constructed from contracted Gaussian-lobe functions. The values D = 0.539 cm-1 and E = 0.031 cm-1 were obtained for the 3A2(n → π*) state and D = -0.588 cm-1 and E = 0.058 cm-1 were obtained for the 3A1 (π → π*) state using the CI wave function constructed from SCF orbitals of the respective parent configurations. An analysis of the effect of CI on the parameters is given for the 3A2 (n n → π*) state of formaldehyde and the 3B1 ground state of methylene. Numerical results are given which show that internally consistent self-consistent field orbitals (ICSCF) are superior to canonical SCF orbitals as a starting point for a CI calculation. Our CI wave function for the 1A1 ground state gave an energy of -114.13658 hartrees which is significantly lower than any previously reported energy calculation. This wave function gives a dipole moment of 2.22 Debye (C+O-) in good agreement with the experimental value of 2.33 ± 0.02 Debye.
    Additional Material: 5 Ill.
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  • 131
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    International Journal of Quantum Chemistry 7 (1973), S. 1039-1043 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 132
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    International Journal of Quantum Chemistry 7 (1973), S. 1063-1075 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have obtained the Bloch spin wave dispersion formula using the methods of spin-free quantum chemistry. The spin-free eigenvectors are waves in spin-free space. This development makes the point that Bloch spin waves are dynamically spin-free. The neutron diffraction transition moment for spin waves is calculated employing the antisymmetrized projections of vector products of spin-free eigenkets and spin kets and is found to be agreement with results of Moorhouse.
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  • 133
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    International Journal of Quantum Chemistry 7 (1973), S. 1099-1116 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The importance sampling method of point selection has been used in the local energy framework to obtain least-squares solutions of the Schrödinger equation for a variety of H2 functions. It is shown that good results are obtainable with relatively small samples, and that the method is rather insensitive within broad limits to the nature of the weighting function employed. Expectation values for a number of operators besides the energy are examined. The energy variances are likewise scrutinized and attempts are made to rationalize their behavior in terms of how and to what extent sample points are chosen.
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  • 134
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    International Journal of Quantum Chemistry 7 (1973), S. 35-49 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One-center core integrals for valence orbitals are determined from the experimental average energies of neutral atomic configurations from Li through Zn. These values are compared with those estimated from CNDO/1, “INDO/1”, CNDO/2, “INDO/2” and with theoretical values calculated from a pseudo-potential method. The agreement is good between values obtained from neutral atoms and from the psuedo-potential calculation except for the 3d orbitals of the transition elements where the theoretically calculated integrals over single ξ functions are not realistic. These two methods reproduce both term and average configuration energies for the first two rows of atoms; the semiempirical method reliably reproduces them for the third row. The CNDO/1 and INDO/1 methods underestimate atomic energies, while the CNDO/2 and INDO/2 procedures fail rather poorly.The propriety of using core integrals estimated semiempirically in molecular orbital calculations is discussed.
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  • 135
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    International Journal of Quantum Chemistry 7 (1973), S. 109-125 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method of direct treatment of valence electrons is proposed for the various 2S, 2P,2D, 2F states of the lithium, sodium, and potassium atoms and the corresponding isoelectronic ions. The function describing the outer electron, which is orthogonal to the wave functions of the electrons in the core, is given as a linear combination of generalized Laguerre functions, with effective charges Q = 1, 2 … equal to the charges of the core.A simpler analytical STO function, with non-integer principal quantum number n is then proposed.
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  • 136
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    International Journal of Quantum Chemistry 7 (1973), S. 135-135 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 137
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    International Journal of Quantum Chemistry 7 (1973), S. 173-186 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equation for the screened potential in the RPA has been derived by using the method of functional differentiation of Martin and Schwinger. The contribution of the “oyster” diagram has been contained in this equation.
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  • 138
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    International Journal of Quantum Chemistry 7 (1973) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 139
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    International Journal of Quantum Chemistry 7 (1973), S. 501-520 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total electronic energy per atom in the lithium metal has been calculated for three different Fermi surfaces as a function of the internuclear distance. In each case the optimized AMO energy as well as the total energy corresponding to doubly filled molecular orbitals (MO) has been calculated. For densities around the equilibrium density the spherical Fermi surface yields the lowest energy whereas a cubic Fermi surface is preferred for low densities. For densities around the equilibrium there is no band splitting: the AMO energy coincides with the MO energy. The computations have been carried out within an LCAO approximation with overlap and multicenter-integrals calculated accurately.
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  • 140
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    International Journal of Quantum Chemistry 7 (1973), S. 745-757 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The exchange polarization energy for the H2+ ion is expressed as an infinite sum of its angular components. At large internuclear distances R, a particular l-component, referred to as induced 2l-pole exchange energy, behaves asymptotically like \documentclass{article}\pagestyle{empty}\begin{document}$$- \frac{4}{{\left({l + 1} \right)\left({l + 2} \right)\left({l + 3} \right)\left({l + 4} \right)}}Re^{ - R}$$\end{document}For larger R this suggests a rather slow l-4 rate of convergence of the series. However, as contrasted to the analogous expansion for the induction energy the convergence speeds up considerably with decreasing internuclear separation.It is also shown that at sufficiently large R a given induced 2l-pole exchange energy can be computed with a high accuracy using a polarization function obtained with neglect of charge overlap effects. Near the bottom of the van der Waals minimum over 99% of the exchange polarization energy can be produced using this simplified form of the polarization function.
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  • 141
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: H2+-type elliptical orbitals are defined in Section 1. These orbitals, which in elliptical coordinates involve a factor (1 + ξ)σ, are employed in variational calculations on the ground states of H2+ and H2 (Sections 2 and 3). Various choices of σ are explored for H2+, while two choices are used for H2 : the “boundary condition” (Equation 6) and the “cusp condition” (Equation 9) values. Variational energies are calculated and compared to the results of similar calculations. Section 3 concludes by employing the H2+-type orbitals in LCETO-MO-SCF calculations on the ground states of H2 and He2++. For both molecules a four-function basis set with two (nonlinear) variational parameters yields more than 99% of the Hartree-Fock limit. Section 4 deals with LCETO-MO-SCF calculations on triangular H3+. Three four-function basis sets are used, and the best energy is -1.2306 a.u., which is in reasonable agreement with the Hartree-Fock limit, -1.2999 a.u. Our best basis set is a four-term two-center expansion of the wave function with only one nonlinear variational parameter. Section 5 concludes the paper with a summary of the methods used to evaluate the integrals which arise in SCF calculations in the H2+-type elliptical orbital basis.
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  • 142
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    International Journal of Quantum Chemistry 7 (1973), S. 877-892 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dispersion interaction between two nonoverlapping atoms (or molecules) is expressed in terms of single-atom “polarizabilities.” The formulation is valid even if one atom (or both) is in an excited state. To illustrate the procedure, the dispersion interaction between a 1s and a 2s hydrogen atom is computed accurately through order R-10 (R = internuclear separation).
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  • 143
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Un procédé de minimisation directe de l'énergie d'une molécule par rapport aux coefficients des orbitales atomiques des fonctions moléculaires est utilisé en vue de déterminer les fonctions de l'état fondamental et des états excités. L'orthogonalité entre les divers états est obtenue par des conditions moins restrictives que celles de Roothaan, si bien que l'énergie obtenue pour la première transition électronique est abaissée: de 0,1 à 0,2 eV pour les transitions π → π* des polyènes.
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  • 144
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    International Journal of Quantum Chemistry 7 (1973), S. 985-989 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spin rearrangement of π-electrons in the ground state of a conjugated molecule in a strong magnetic field H is discussed. The spin S of the molecule increases as the field H increases (intramolecular paramagnetism). The dependence S(H) for linear and cyclic conjugated molecules in the free-electron model and in the Hückel-London approximation is derived. For the cyclic molecules the diamagnetic effects are taken into account.
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  • 145
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    International Journal of Quantum Chemistry 7 (1973), S. 1029-1031 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 146
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    International Journal of Quantum Chemistry 7 (1973), S. 1033-1035 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 147
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    International Journal of Quantum Chemistry 7 (1973), S. 905-925 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydroxyl diffusion and interhydroxyl binding in hydroxyapatite has been studied. LCGO-MO-SCF calculations have been carried out on groups of hydroxyl ions in a perfect and a vacancy-containing crystal.Electrostatic crystal effects were accounted for by including the crystal potential field in the SCF calculations. Nearest-neighbour interactions were calculated to first order. Effects exerted by fluorine impurities were considered for the vacancy-containing crystal.The calculations indicate that narrow bandwidths obtained in nmr experiments on biological hydroxyapatite may be caused by a hydroxyl displacement mechanism and that no interhydroxyl hydrogen bonds exist in hydroxyapatite. The suggestion that the caries-inhibiting properties of fluorine impurities in human dental enamel is caused by a diffusion-binding mechanism is supported by the results.
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  • 148
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    International Journal of Quantum Chemistry 7 (1973), S. 959-970 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Very often only “diagonal” second order energies, varying as an even power of R-1, occur in the multipole expansion of the interaction energy. However for many molecular interactions important “nondiagonal” second order energies, varying as an odd or even power of R-1 can arise. This point is emphasized by a general discussion and by a detailed specific example, the interaction of an ionized dipolar molecule with a nondegenerate atom. Also some useful theorems, on the orientation average of various types of second order energies, are derived.
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  • 149
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    International Journal of Quantum Chemistry 7 (1973), S. 1021-1028 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The general formula for the electron-electron repulsion integral in the modified Cartesian Gaussian basis set derived in Ref. [1] is simplified. A general relation between the standard and modified CG functions is given. A possible use of the modified CG functions to quantum chemical calculations which include the correlation factor rij2 is indicated.
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  • 150
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 151
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    International Journal of Quantum Chemistry 7 (1973), S. 309-318 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: SCF calculations utilizing a basis of all s-type Gaussians have been performed to investigate the dimerization of BH3 to B2H6. Localized molecular orbitals and pseudonatural orbitals are calculated. The dimerization energy obtained (11.5 kcal/mole) supports the assumption that the non-Hartree-Fock interactions (electron correlation) play a dominant role (Exp = 40-60 kcal/mole).The energy of the principal type of resonance structure based on the SCF-MO's of the separated-but-distorted BH3 systems is rigorously calculated and found to be 150 kcal/mole higher in energy than the SCF energy of B2H6. Thus, resonance stabilization (delocalization) is shown to be extremely important to the stability of the “three-center” bonds in B2H6, as has been suspected for many years.
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  • 152
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    International Journal of Quantum Chemistry 7 (1973), S. 357-364 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe a method to optimize simultaneously Slater orbital exponents. The procedure is based on Newton's method and requires the derivatives of the energy as a function of the exponents. The calculation of these derivatives is described explicitly. The method has been applied to the hydrogen molecule.
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  • 153
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    International Journal of Quantum Chemistry 7 (1973), S. 405-406 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 154
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    International Journal of Quantum Chemistry 7 (1973), S. 407-409 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 155
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    International Journal of Quantum Chemistry 7 (1973), S. 475-490 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nonempirical molecular orbital calculations of the energies of CH3CH2+ (ethylcarbonium ion) and HOCH2+ (hydroxymethylcarbonium ion) as a function of rotation about the C—C or C—O bonds and deviation from coplanarity at the carbonium ion center are reported. As expected, and in agreement with previous work, both carbonium centers are planar and there is no barrier to rotation in the planar ethylcarbonium ion. However, for the planar configuration at carbon, the conjugative interaction between oxygen and carbon produces a barrier to rotation about the C—O bond of HOCH2+ of 19.6 Kcal/mole.When a pyramidal geometry is imposed upon the carbonium ion center of CH3CH2+, a typical three-fold barrier results. As the deviation from coplanarity increases there is a regular increase in the barrier height (1.72 Kcal/mole at the tetrahedral geometry), but the energy minimum remains at the same position in each case (60°). For HOCH2+, imposition of a pyramidal geometry on the carbonium ion center causes a change in both rotational barriers. One decreases slightly (from 19.6 to 15.4 Kcal/mole) and the other increases to 30.5 Kcal/mole. There is an accompanying change in the position of the minimum of the rotational potential, from 90° towards the gauche structure.
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  • 156
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    International Journal of Quantum Chemistry 7 (1973), S. 537-546 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is given for accurate calculation of the expectation value of the Hamiltonian of a crystal with respect to a single-determinant wave function of LCAO type. The method is partly based on numerical integration over one Wigner-Seitz cell. In principle, the calculations involve infinite summations over lattice sites; suitable truncation methods are devised.
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  • 157
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    International Journal of Quantum Chemistry 7 (1973), S. 583-608 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The (spin projected) extended Hartree-Fock equations are derived and discussed in the general (“many λi”) case. The derivation is based on the corresponding generalized Brillouin theorem, substituting in its expression the spin projected DODS Slater determinant as a linear combination of determinants. The expressions obtained for the elements of the different matrices εcd (c = a or b, and d = a or b) occurring in the equations are analyzed. The transformation of the equations into the form of a pseudoeigenvalue problem and the LCAO form of the equations are given, too. Finally the relation to the Goddard's GF equations is discussed in detail.
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    International Journal of Quantum Chemistry 7 (1973), S. 75-85 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described whereby molecular symmetry properties may be used to reduce the numbers of one- and two-electron integrals that need to be calculated and stored in the course of a molecular SCF calculation. The method is a generalization of a previously reported procedure, extending the earlier work to cover those molecules belonging to point groups which have complex representations. The practical application of the method is discussed and an illustrative example given. The quite extensive tables of molecular symmetry properties which the method uses may be computer generated in a straightforward manner. A procedure for doing this using a minimum amount of input data is presented.
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    International Journal of Quantum Chemistry 7 (1973), S. 1037-1037 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 160
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    International Journal of Quantum Chemistry 7 (1973), S. 1091-1097 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The restriction on a method for computing irreducible representations of finite groups, requiring that in the irreducible representation to be constructed, at least one group element has at least one nondegenerate eigenvalue, is removed. The method is thus shown to be applicable to an arbitrary finite group and constitutes a practical algorithm for handling groups of order less than 400.
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  • 161
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    International Journal of Quantum Chemistry 7 (1973), S. 1139-1144 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general method is given for finding the complete set of linearly independent crystal field parameters from symmetry arguments. No recourse is made to expansions of the crystal field in terms of spherical harmonics. The core of the method lies in an extension of the known zero-trace property of tensor operators, to the case of irreducible operators.
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  • 162
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    International Journal of Quantum Chemistry 7 (1973), S. 1193-1201 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Padé approximants of type II have been applied to solve equations of the type F(z) = 0. The method is compared with the first-order iteration procedure, the Aitken-Samuelson formula, and the Newton-Raphson tangential method. As a test example the partitioning technique in its most simple form is applied to the Hamiltonian of a rigid symmetric-top molecule in a static electric field. The proposed algorithm is found to be superior to the first-order procedure and the Aitken-Samuleson formula, and at least as effective as the Newton-Raphson method.
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    International Journal of Quantum Chemistry 7 (1973), S. 1221-1225 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 164
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    International Journal of Quantum Chemistry 7 (1973), S. 365-381 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mathematical analysis is presented of molecular integrals of relativistic interactions in molecules. The integrals are based on Gaussian-type orbitals and include those arising from variation of electron mass with velocity, one-electron Fermi contact interaction, electron spin-same-orbit interaction, electron spin-nuclear spin interaction, electron spin-spin contact interaction, electron spin-other-orbit interaction, electron spin-spin dipolar interaction and electron orbit-orbit interaction. The integrals are expressed in suitable forms for use in computer. It is also pointed out that the integrals are written essentially in terms of the overlap, nuclear attraction, electron repulsion, or field integrals.
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  • 165
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    International Journal of Quantum Chemistry 7 (1973), S. 425-457 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: All the second-order density matrix spin components for the spin-extended Hartree-Fock method are obtained. The coefficients in the final formulae are only ωsM, ωsM±1, ωsM±2, where ωsM are the weights of pure states of spin s in the initial unprojected determinant with spin projection M. The eigenvalue problem for the best electron density natural orbitals in the spin-extended method is formulated. All the second-order transition density matrix spin components between pure spin basis functions built of orthogonal orbitals and distinguished by different core choice are also found. This basis may be used on CI calculations.
    Additional Material: 5 Tab.
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    International Journal of Quantum Chemistry 7 (1973), S. 491-499 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Uniform field quadrupole polarizabilities and shielding factors of the first three ions of 2-, 3-, and 4-electron sequences in their ground states have been calculated in the coupled Hartree-Fock (CHF) scheme. For comparison the uncoupled Hartree-Fock (UHF) results are also presented. It is observed that the uniform field quadrupole polarizabilities differ slightly in the two schemes and agree well with the UHF results of Lyons, Langhoff and Hurst. However the shielding factors differ appreciably in the two schemes and are completely different from those of Lyons et al. The cause of the difference in the shielding factor values is investigated.
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  • 167
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    International Journal of Quantum Chemistry 7 (1973), S. 1183-1192 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selected valence electron split-shell molecular orbital calculations have been performed on the diatomic interhalogen molecules in order to obtain their binding energies, equilibrium internuclear distances, vibrational force constants, dipole moments and nuclear quadrupole coupling constants. The results are compared with the corresponding closedshell values and with those of some previous semiempirical and nonempirical all valence electron calculations. It is observed that the selected valence electron split-shell molecular orbital method which involves the least amount of computations yields results in better agreement with experiment than other methods.
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  • 168
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    International Journal of Quantum Chemistry 7 (1973), S. 1221-1221 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 169
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    International Journal of Quantum Chemistry 7 (1973), S. 215-222 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical study of π-electron spin density distributions has been made for a series of fluoro-substituted hydrocarbon radical cations using unrestricted Hartree-Fock theory. Although some of the predicted proton splittings are not in very good agreement with experiment, the overall agreement with experiment can be passed as fairly satisfactory considering the approximate nature of the theory used. The experimental fluorine splittings can be well predicted by using a one-parameter relationship between the isotropic fluorine splitting (aF) and the π-electron spin density (ρCC) on the attached carbon. It has been further shown that both ρCC and the proportionality constant (Qeff) in the linear relation, are fairly insensitive to the parameter choice.
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  • 170
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    International Journal of Quantum Chemistry 7 (1973), S. 319-332 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tunneling of a hydrogen atom through the barrier of a three-dimensional double-well potential is considered. From the time-dependent Schrödinger equation, expressions are derived for the ensemble-averaged probability density and for the probability that the hydrogen atom is in the reactant region, in the barrier region, or in the product region. It is found that when thermal vibrations are not taken into account, the ensemble-averaged probability density may oscillate with time about its equilibrium value. When thermal vibrations are included, the oscillations become damped and the probability density approaches equilibrium. The tunneling rate is found to decrease considerably for increasing barrier thickness and barrier height.
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  • 171
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    International Journal of Quantum Chemistry 7 (1973), S. 1045-1050 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The general problem of the transfer of the representation of a set of orthonormal functions from one basis to a different, nonequivalent one is considered and specialized to a matrix formulation convenient for use in molecular electronic structure calculations. A procedure is suggested for treating problems where the transfer of representation breaks into a subset of most interest and one of less interest as for example the occupied and virtual orbitals of a Hartree-Fock SCF calculation. These techniques are then applied to obtain a representation of a methyl group from an SCF wave function for methane.
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  • 172
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    International Journal of Quantum Chemistry 7 (1973), S. 1117-1137 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of Lie algebras in quantum chemistry is considered. Particular attention is devoted to their application to high symmetry problems especially where icosahedral symmetry prevails. A general programme for implementing the theory of Lie algebras in the analysis of symmetry problems is outlined.
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  • 173
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    International Journal of Quantum Chemistry 7 (1973), S. 1145-1158 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Schrödinger equation of an N-electron closed-shell system is reduced to that for the spatial wave function Ψ∥[λ] by the aid of the theory of the symmetric (permutation) group SN. The first-order perturbation equation based on the Hartree-Fock-SCF model as the zero-order solution is then solved by decomposing it into a set of soluble 1/2(N/2)[(N/2) + 1] equations for the pair-correlation (first-order) spatial wave functions. These spatial functions give the spatial parts of the pair functions in the spin orbital basis formulation, reducing also the number of independent pairs needed in the first order.
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  • 174
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    International Journal of Quantum Chemistry 7 (1973), S. 1159-1174 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formulation developed in Paper I for a closed shell system is extended for a system with one nonclosed shell. Roothaan's restricted Hartree-Fock (RHF) open-shell wave function is taken as the zero-order solution. The first-order Schrödinger equation is then solved for the spatial part of the wave function by reducing it to a set of one- and two-electron equations, using the properties of the symmetric group SN.
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  • 175
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 395-411 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The design and implementation of software for real-time spectral analysis on an IBM 1130 with 8k core is described. The procedures for estimation of coherence and cross-spectra are discussed in detail.
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  • 176
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 381-394 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The Fast Fourier Transform is employed as a method of Laplace transform inversion to solve problems in the civil engineering fields of visco-elasticity and hydrology. When these problems are accurately represented by a linear time-invariant model, it is shown that the Fast Fourier Transform inversion procedure is often more accurate than standard convolution and inversion techniques. The speed and accuracy of solution resulting from this application of the Fast Fourier Transform is illustrated by referring to case studies solved on an IBM 1130 computer, model 3D processor with 32K memory.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 427-439 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Stress fields near crack tips in an elastic body can be specified by the stress intensity factors which are closely related to the stress singularities arising from the crack tips. These singularities, however, cannot be represented exactly by conventional finite element models. A new method for the analysis of stresses around cracks is proposed in this paper on the basis of the superposition of analytical and finite element solutions. This method is applied to several two-dimensional problems whose solutions are obtained analytically, and it is shown that their numerical results are in excellent agreement with analytical ones. Sufficiently accurate results can be obtained by the conventional finite element analysis with rather coarse mesh subdivision. Computational efforts are then considerably reduced compared with other methods.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 447-447 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 454-456 
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    Keywords: Engineering ; Engineering General
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 456-456 
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    Keywords: Engineering ; Engineering General
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  • 181
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 467-473 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A generalized variational principle is presented, which leads to a modified finite element approach for three-dimensional field problems. Both, potential function and velocity field, are approximated by expansions which are continuous across the inter-element boundaries. The rapid convergence of this mixed model is shown by two examples.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 497-509 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A computer program for the in-core solution of large, sparse, unsymmetric systems of linear equations is presented in this paper. The program employs elimination techniques for solution of systems of linear equations. A limited number of zeros is stored and trivial arithmetic is by-passed to preserve computer storage and to reduce the time required for solution. Several techniques for selecting the pivotal elements are discussed and their effect on accuracy and computational time are examined.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 521-527 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Numerical methods are used to investigate the two-dimensional motion of a viscous incompressible fluid impulsively started past a flat plate of finite breadth at zero incidence to the uniform motion of the fluid at large distances from the plate. A step by step integration in time of Helmholtz's vorticity equation is used for Reynolds numbers 10-500.The magnetohydrodynamic case is also considered with the applied magnetic field at infinity parallel to the uniform stream and the non-conducting plate. Results for the Magnetic Reynolds number 50 and infinite, Viscous Reynolds number 50 and 0≤β≤2, where β is the ratio of the square of the Alfvén speed to the square of the main stream velocity, are presented.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 608-608 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 185
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 43-55 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A new family of triangular finite elements is described, useful for solving the axisymmetric vector Helmholtz equation, and a variety of scalar Helmholtz equation problems which lead to generalized Bessel equations of some order m. This family is similar in principle to the scalar axisymmetric Helmholtz elements derived earlier, but requires both reformulation of its describing equations and corresponding new universal element matrices, for successful computational implementation. The necessary formulation is given in this paper. Matrix elements to the sixth-order inclusive have been calculated and extensively tested computationally.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 57-67 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The criteria for stability of the explicit finite difference solution of the one-dimensional, transient, conduction heat transfer problem with both radiant and convection heat transfer at the boundaries are considered in this paper. These criteria are governed by an inequality set from a functional relationship between the newly calculated and the old temperature at each node.From the node with the most stringent criteria, it is shown that setting the coefficient of the old temperature equal to zero in the governing difference equation is not sufficient for a general criterion. On the other hand, setting the derivative of the new temperature with respect to the old temperature equal to zero in the governing difference equation presents a simple, straightforward technique for obtaining a sufficient condition for a stable system. It is further shown that the second law of thermodynamics, written in explicit finite difference form, does present a necessary criterion for stability. However, the second law, because it is in the form of an inequality, does not present as simple a criterion as the derivative method does.The specific problem studied is a finite thickness slab, initially at a uniform temperature, but instantaneously subjected to both radiation and convection on its two surfaces. Temperature profiles were calculated on a digital computer and are presented in dimensionless graphical form over a range of five dimensionless parameters. A plot that relates stability to the maximum time-step size for the entire range of practical conditions of radiation numbers is also presented.
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    International Journal for Numerical Methods in Engineering 7 (1973) 
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    Keywords: Engineering ; Engineering General
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  • 188
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 117-124 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A theorem expressing geometric conditions necessary and sufficient for the stiff stability of a linear multistep method is obtained. A corollary to this theorem provides sufficient conditions for stiff stability, for the class of algorithms characterized by a single essential root. By applying the Schur-Cohn criterion and employing a computerized algebraic manipulation program, the result provides a first step towards an exhaustive search technique for determining a continuum of members of this class.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 175-183 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A method is described for the solution of large sets of sparse equations arising in structural analysis. This method, called partial elimination, combines the concepts of elimination and iteration in such a way that good convergence rates can be obtained using a computer storage space not much greater than that required for other iterative methods.
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  • 190
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 211-223 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A survey of recent developments in sparse matrix technology is presented. Two fundamental areas are reviewed: 1.Sorting and reordering techniques by which the non-zero elements of a given sparse matrix can be rearranged to obtain a form which leads to more efficient computations.2.Direct methods for solving systems of linear equations and computing inverses.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 240-240 
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    Keywords: Engineering ; Engineering General
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  • 192
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 155-173 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The present investigation examines the multibar truss optimization problem in the context of a general class of unconstrained optimization procedures in conjunction with various types of penalty function transformations. Specifically, the problem is transformed into a series of unconstrained minimization problems using the penalty function techniques of Heaviside and SUMT. These are solved using the methods of Rosenbrock (orthogonal directions), Powell (conjugate directions) and Nelder-Mead (Simplex). This resulted in many cases in substantial improvements being recorded over previously reported data. The paper includes a comparative study of the synthesis based on these procedures.
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  • 193
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 461-477 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Computer-oriented mesh generators, which serve as pre-processors to finite element programs, have recently been developed by several investigators to alleviate the frustration and to reduce the amount of time involved in the tedious manual subdividing of a complex structure into finite elements. Our purpose here is to describe how the techniques of bivariate ‘blending-function’ interpolation, which were originally developed for, and applied to, geometric problems of computer-aided design and numerically controlled machining of free-form surfaces such as automobile exterior panels, can be adapted and applied to the problems of mesh generation for finite element analyses. We concentrate attention on the problem of curvilinearly co-ordinating simply connected planar domains R by constructing invertible maps of the unit square S ≡[0, 1] × [0, 1] onto R. Extensions of the methods described herein to shells in 3-space is straightforward and is illustrated by a practical example taken from the automobile industry. Analogous mesh generators for three-dimensional solids can be developed on the basis of the trivariate ‘blending-function’ formulae found at the end of the second section.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 309-323 
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Various solutions of laminated plates by the finite element method are analysed. An efficient solution of skew (or rectangular) laminated plates with small effect of σz and ∊z stress and strain components is developed. It can be used with an arbitrary number of layer elements (sub-elements) in different plate elements. Some remarks to the possible modification of solution are presented. Numerical examples with a short discussion and conclusions complete the paper.
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    Notes: The hybrid-element concept and the complex variable technique have been adopted for constructing a special super-element to be used jointly with conventional finite elements for the analysis of elastic stress intensity factors for plane cracks. The use of the complex variable technique permits the proper consideration of the stress intensity at the crack tip, and it also leads to very efficient programming. The use of such a super-element in the finite element solution has been shown to be highly accurate when only a very coarse element mesh is used near the crack.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 345-355 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Consider a solid heat conductor with a non-linear constitutive equation for the heat flux. If the material is anisotropic and inhomogeneous, the heat conduction equation to be satisfied by the temperature field θ(x, t) is, \documentclass{article}\pagestyle{empty}\begin{document}$$ \rho c\frac{{\partial \theta }}{{\partial t}} = {\rm div}({\rm L}(\theta,{\rm x})[{\rm grad}\theta]) + q $$\end{document} Here L(θ, x) [grad θ] is a vector-valued function of θ, x, grad θ which is linear in grad θ, In the present paper, the application of the finite element method to the solution of this class of problems is demonstrated. General discrete models are developed which enable approximate solutions to be obtained for arbitrary three-dimensional regions and the following boundary and initial conditions: (a) prescribed surface temperature, (b) prescribed heat flux at the surface and (c) linear heat transfer at the surface. Numerical examples involve a homogeneous solid with a dimensionless temperature-diffusivity curve of the form κ = κ0(l + σT). The resulting system of non-linear differential equations is integrated numerically.
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    International Journal for Numerical Methods in Engineering 7 (1973), S. 405-408 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Several formulas are presented for the numerical integration of a function over a triangular area. The formulas are of the Gaussian type and are fully symmetric with respect to the three vertices of the triangle.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 413-425 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A limitation of most plate and shell discrete elements now in use is the shape of their undeformed geometry. Typically, the plan form of these elements is a straight-sided triangle or quadrilateral that linearly approximates the undeformed geometry while often using higher-order polynomials to approximate the deformed geometry. This modelling difference leads to inefficiencies that can be eliminated, as demonstrated by a new parametric discrete element based entirely on bicubic Hermite polynomials. This representation of element geometry corresponds to the bicubic Coon's surface patch widely used in design, which allows a common mathematical model for design and analysis. Consideration is given to automating the generation of these patches. Solutions are presented for several plate bending and plate stretching problems. The solutions are in good agreement with closed-form solutions and photoelastic results in the case of a stress-concentration problem. These data demonstrate that the new parametric discrete element maintains solution accuracy for plates with curved boundaries.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 443-446 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper compares the results obtained by the finite element method with ‘exact’ solutions to a given set of problems. These are the stresses on the boundary of a hole in an infinite plate, the plate being subjected to three different types of loading. Two types of element are used for these plane stress problems, triangular elements with constant strains and tri- angular elements with linearly varying strains. The problems are solved for two different meshes and the results shown are stresses along a radial section and the values derived for stress concentrations against the number of unknowns in each mesh.
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    International Journal for Numerical Methods in Engineering 6 (1973), S. 446-447 
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    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Additional Material: 1 Ill.
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