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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 11 (1977), S. 189-211 
    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 theory of pth-order singular differential equations is adaptable to the study of the system of recurrence relations occurring in the problem of a one-dimensional chain with pth-neighbor interactions. By using Green's formula, a mapping is defined between the space Vn of eigenvectors to the dynamical matrix and the symplectic space V2p of boundary conditions for the recurrence equations. The properties of the resolvent are obtained from an analysis of the solutions of a system of inhomogeneous equations and Green's matrix is constructed for the case of standard Sturm-Liouvilletype boundary conditions. The Weyl surface is discussed and its properties used for the construction of square summable sequences which in turn can be employed in expansion formulas. The generalization of Weyl's m-function in the second-order case (p = 1) becomes for p ≥ 2 a p × p matrix M(λ), where λ is a complex parameter. The imaginary part Im {M(λ)} is related to the spectral properties and serves as basis for the discussion of different concepts of spectral density for the normal modes of lattice dynamical problems. An important practical result is the equation M = -Ψa-1Φa valid in the limit point case, generalizing the corresponding second-order formula.
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  • 2
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    International Journal of Quantum Chemistry 11 (1977), S. 271-276 
    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 electrostatic correction to the energy of the EH method is deduced from the Hartree energy. A recent correction, due to Anderson and Hoffmann, is easily deduced as a particular case. Some calculations show how the correction can improve the description of stretching problems by EH calculations but poor results are obtained in bending and torsion problems.
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  • 3
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    International Journal of Quantum Chemistry 11 (1977), S. 317-324 
    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 basis set dependency of the core ionization potential of water was investigated for atomic optimized Cartesian Gaussian basis sets. Basis set parameters optimized for oxygen yielded better IP's than basis set parameters optimized for fluorine. Not much was gained by using different parameters for the ground state and for the 1s hole state.
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  • 4
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    International Journal of Quantum Chemistry 11 (1977), S. 325-339 
    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 recursive numerical integration scheme based on the method of Clenshaw and Curtis is proposed for the efficient implementation of the variation-iteration procedure for the computation of approximate energies and wave functions for atomic systems. Extensive numerical tests are carried out to assess the accuracy and efficiency of the method and inaccuracies in some earlier calculations are pointed out.
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  • 5
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    International Journal of Quantum Chemistry 11 (1977), S. 359-379 
    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 formalism described in the first paper of this series is applied to the chain SU(2) ⊃ D′∞ ⊃ D′4 ⊃ D′2, the covering of SO(3) ⊃ D∞ ⊃ D4 ⊃ D2. The state vectors (|αJaΓγ) adapted to each link of the chain under consideration and the corresponding coupling coefficients \documentclass{article}\pagestyle{empty}\begin{document}$ f\left( {\begin{array}{*{20}c} {J_1 } & {J_2 } & J \\ {a_1 \Gamma _1 \gamma _1 } & {a_2 \Gamma _2 \gamma _2 } & {a\Gamma \gamma } \\ \end{array}} \right) $\end{document} are given in analytical form. The material reported here is very convenient for a quantum-mechanical description of molecular and nuclear systems with linear, tetragonal, or orthorhombic symmetry. In this respect, we present an outline for its applications to the electronic and vibrational-rotational spectroscopy of molecular aggregates and to the rotational spectroscopy of molecules or nuclei. In addition, we briefly show how the material may simplify the second-order non-Lie subgroup type approach to the representation theory of SU(2).
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  • 6
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    International Journal of Quantum Chemistry 11 (1977), S. 415-425 
    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 transferability of bonds in a set of small molecules has been explored. The molecular wave-functions have been calculated from the group (or loge) function method, via a construction based on Gaussian functions. The transferability is very good and the effect of lone pairs on adjacent bonds has been analysed. Furthermore, a very simple procedure has been proposed to estimate the frontiers of the bonds.
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  • 7
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    International Journal of Quantum Chemistry 11 (1977), S. 441-450 
    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 series of LCAO-MO-SCF calculations, using various basis sets of Gaussian-type functions, has been made in order to study the effects of p, d, and f polarization functions for a 10-electron isoelectronic series of oxygen hydrides and for an 18-electron isoelectronic series of sulfur hydrides. Conclusions from these results suggest that meaningful proton affinities cannot be calculated without the inclusion of a d function on the heavy atom and a p function on the hydrogen atoms.
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  • 8
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    International Journal of Quantum Chemistry 11 (1977) 
    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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  • 9
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    International Journal of Quantum Chemistry 11 (1977), S. 759-766 
    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 two-parameter ω-technique for MO calculations is proposed. The parameters ω and ω′ are chosen empirically to obtain a good agreement between calculated and observed bond lengths. The method amounts to an inclusion of the effect of nearest-neighbour electronic repulsion integrals into the conventional ω-technique.
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  • 10
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    International Journal of Quantum Chemistry 11 (1977), S. 907-916 
    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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  • 11
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    International Journal of Quantum Chemistry 11 (1977), S. 1001-1004 
    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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  • 12
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    International Journal of Quantum Chemistry 11 (1977), S. 1043-1043 
    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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  • 13
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    International Journal of Quantum Chemistry 12 (1977), S. 593-608 
    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: Floating spherical Gaussian orbital (FSGO) open-shell calculations have been made to determine the potential energy surface of planar square and rectangular arrangements of the four-electron system H4. This surface is discussed in relation to the bimolecular isotope exchange reaction H2+D2-→ 2HD. The changes in energy and geometry accompanying the coplanar approach of two hydrogen molecules interacting chemically have also been investigated. Calculations on the electronic energies of planar T-shaped and kite arrangements of H4 of various sizes show that it is unlikely that these configurations can serve as transition states for the exchange reaction. However, the energy curve for linear configurations of H4 (H—H—H … H), calculated as a function of the H3 … H distance with the symmetric linear H3 (H-H-H) unit fixed at the internuclear distance of 1.9080 a.u., is found to have a deep minimum (-1.9176 a.u.) at an r(H3 … H) distance of 1.5846 a.u. The overall results suggest that the following mechanism for the exchange reaction, H2+H2→H2+H+H→H3+H→H+H2+ H→H2+H2 could be advantageous as it requires a barrier height of 0.1604 a.u. which is significantly lower than that calculated from the saddle point energy (0.1950 a.u.). However, the problem of reconciling this with the experimental activation energy of 0.0685 a.u. still remains.
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  • 14
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    International Journal of Quantum Chemistry 12 (1977), S. 655-670 
    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: Excitation energies and transition moments have been determined from a second order polarization propagator and the effect of including energy shifted denominators has been investigated. Results for Be and CH+ show a change of 2-5% for the transition moments and of 0-20% for the singlet excitation energies in a second order approach compared to a first order (time-dependent Hartree-Fock) approximation. Both Be and CH+ are triplet unstable in the time-dependent Hartree-Fock approximation. The triplet instability is removed for Be but not for CH+ in a second order polarization propagator approach.
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  • 15
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    International Journal of Quantum Chemistry 12 (1977), S. 759-763 
    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 spherical limit of a single particle in the field of three nuclei is shown to exhibit a variety of phenomena associated with the stability of the various extrema involved. Some consequences with respect to the general problem of detecting broken symmetry solutions of variational problems are pointed out.
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  • 16
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    International Journal of Quantum Chemistry 11 (1977), S. 895-895 
    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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  • 17
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    International Journal of Quantum Chemistry 11 (1977), S. 931-941 
    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 of the variants of Löwdin's partitioning technique that makes use of a Brillouin-type perturbation expansion for the study of lower bounds to the eigenvalues of a Hamiltonian has not been applied to any practical quantum mechanical problem so far. To illustrate how powerful this method can be, an application is made to the rigid rotator in an electric field, which has already been studied by Choi and Smith using the bracketing function of an intermediate Hamiltonian. It turns out that for a given order of the basis set of the Bazley space the Brillouin-Löwdin perturbation expansion gives closer bounds than the method of Choi and Smith, except for the case l = m, where the procedures can be shown to be mathematically equivalent. Especially for high l - m the number of basis functions needed to attain the same accuracy is by far larger for the method of Choi and Smith than for the Brillouin-Löwdin method.
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  • 18
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    International Journal of Quantum Chemistry 11 (1977), S. 991-1000 
    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 solution of the quantum-mechanical one-particle problem involving a Coulomb potential with a cut-off contains Whittaker functions, difficult to evaluate individually. However, the energy expression involves a ratio of two contiguous Whittaker functions, and the entire ratio is easily expressed as a convergent continued fraction. Representative energy eigenvalues are calculated, correcting the errors due to an earlier Bessel function approximation by Wannier.
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  • 19
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    International Journal of Quantum Chemistry 13 (1978), S. 391-410 
    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 model consisting of a harmonic oscillator well and a repulsive inverse square potential, coupled by a delta function, is solved. We find the S-function for this case and study its poles as a function of the coupling strength. These poles show how the harmonic levels shift and broaden as the two potential curves couple and predissociation occurs. A “new state” is found when the energy threshold is just below the first excited state of the harmonic oscillator.
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  • 20
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    International Journal of Quantum Chemistry 13 (1978), S. 455-456 
    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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  • 21
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    International Journal of Quantum Chemistry 13 (1978), S. 499-507 
    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 thermodynamics of the DNA helix-coil transition is studied, starting from the thermodynamical potential difference between the states helix and coil; this potential difference is understood as the difference in free energies. With only three parameters obtained from experimental data different quantities of the T2 phage DNA molecule are calculated. It is observed that the phase transition is of second order.
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  • 22
    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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  • 23
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    International Journal of Quantum Chemistry 13 (1978) 
    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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  • 24
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    International Journal of Quantum Chemistry 13 (1978), S. 605-617 
    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 very efficient and exact method for calculating the long-range effects in polymers is reported. The method is based on the multipole expansion within the Fock operator, and exact summation up to infinity is carried out. Only a small number of one-electron integrals have to be considered, while in the traditional approach one has to compute a large number of two-electron integrals. Results on LiH model polymer have been obtained with a remarkable accuracy within a negligible computing time.
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  • 25
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    International Journal of Quantum Chemistry 13 (1978), S. 641-677 
    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: Let E(R) be a potential-energy function for a neutral or ionic diatom in the Born-Oppenheimer approximation. Then the approximation of E(R) for 0 〈 R 〈 ∞ starting from finite and typically small sets of given information is considered. The approach is based on the fact that the scaled potential curves F(R) = R2E(R) derive from an eigenvalue problem which depends linearly on R. The nature of the curves F(R) is examined in detail. The results include the discovery of various approximants, some of which display rigorous bounding properties and others, closely related, whose behavior with respect to the approximated function appears to be predictable.
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  • 26
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    International Journal of Quantum Chemistry 13 (1978), S. 679-692 
    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: In an attempt to rationalize and improve an approximate exchange perturbation scheme related to the model of Murrell et al., more accurate approximations are introduced eliminating the use of empirical parameters. The total interaction energy has been evaluated as the sum of additive electrostatic, exchange, charge transfer, and dispersion contributions. It is proven that the assumption of intramolecular ZDO approximation is equivalent to the use of the Mulliken formula for intermolecular intergrals in the region of small overlap. It is also shown that the use of exact two-center resonance integrals and atomic multipole expansion leads to a substantial improvement of results. The method has been applied to calculation of interaction energies of some model hydrogen-bonded complexes of water, hydrogen fluoride, adenine, thymine, guanine, and cytosine using approximate all-valence wave functions.
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  • 27
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    International Journal of Quantum Chemistry 13 (1978), S. 769-775 
    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 problem considered is that of selecting the finite orbital basis which will minimize the energy in a given size CI calculation. (1) A one-body operator is defined which has as eigenfunctions the desired optimal basis. The operator is defined in terms of the basis which leads to a self-consistency problem of Hartree-Fock type. (2) A method of successive orbital rotations is defined which is shown to have desirable convergence properties.
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  • 28
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    International Journal of Quantum Chemistry 11 (1977), S. 380-380 
    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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  • 29
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    International Journal of Quantum Chemistry 13 (1978), S. 160-160 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
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  • 30
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    International Journal of Quantum Chemistry 13 (1978), S. 199-206 
    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 that application of the orthonormality-constrained variation method to the absolute squares of three kinds of overlap integrals leads to eigenvalue equations and of which the eigenvectors belonging to maximum (minimum) eigenvalues are the maximum (minimum) overlap, localized, and hybrid orbitals. In the eigenvalue equations, coupling operators similar to those used in SCF theory are found to occur. Connection of the maximum orbitals to a many-shell model, a simple MO theory, and Löwdin's orthonormalization is also discussed.
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    International Journal of Quantum Chemistry 13 (1978), S. 235-238 
    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: Electric polarizabilities are calculated by solving the first- and second-order perturbation equations through a variational procedure. Satisfactory numerical results are obtained for a number of molecules using the CNDO approximation with an extended basis set.
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  • 32
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    International Journal of Quantum Chemistry 14 (1978), S. 209-212 
    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 mathematical basis for the Ruedenberg's and Mulliken's approximations is given in a general framework.
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    International Journal of Quantum Chemistry 14 (1978), S. 239-243 
    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 ab initio Hartree-Fock crystal orbital method is used for the calculation of the energy band structure of a one-dimensional model of (SN)x. Two energy band structures are described corresponding to the self-consistent spin density wave (SDW) and the self-consistent charge density wave (CDW) solution, respectively.
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  • 34
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    International Journal of Quantum Chemistry 13 (1978), S. 367-374 
    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 multiple scattering molecular orbital method, with different choices of sphere radii and local exchange, is applied to the cluster CrF63-. The orbital energies are almost always in the same order but uniformly moved up or down the energy scale depending on which parameters are used. Charge densities are only slightly dependent on the parameters. A method to avoid interaction with Rydberg-like states is suggested.
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  • 35
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    International Journal of Quantum Chemistry 13 (1978), S. 411-428 
    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 general quantum-mechanical description of molecular transport across biological membranes has been developed. The one-dimensional Schrödinger equation for the motion of ions and molecules across the biological membrane has been solved using reasonable potential barriers. Two types of potential profiles for such transports have been considered: a flat barrier proposed by Hall et al. for lipids and an oscillatory potential proposed by Lauger for lipids and by us in this paper for intrinsic proteins. The general behavior of the transmission coefficient as a function of energy and the variation of the permeability as a function of structural changes in the membrane have been discussed. Finally, the importance and areas of applicability of such a theory have been pointed out.
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    International Journal of Quantum Chemistry 14 (1978), S. III 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
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    International Journal of Quantum Chemistry 13 (1978), S. 483-497 
    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: Le découpage de la densité électronique totale dans une molécule, en contributions provenant des diverses orbitales, permet de définir des régions orbitalaires de caractère conventionnel dont la charge totale est égale à la somme des populations de Mulliken des orbitales constituant les diverses régions. La fluctuation relative de la charge de ces régions s'exprime simplement en fonction des populations de Mulliken et des indices de liaisons. Cette analyse de la densité dans des molécules variées (saturées ou conjuguées) permet de retrouver les liaisons chimiques de la graphie classique comme correspondant à des régions orbitalaires de charge voisine de 2 et présentant une fluctuation relative fiable (≤0, 10). Compte tenu du caractère dynamique que contient la notion de liaison, les résultats obtenus trouveraient une interprétation simple dans l'espace des phases. L'impuissance de la Mécanique quantique de donner une description dans cet espace expliquerait l'impossibilité de déduire de calculs quantiques la notion měme de liaison chimique.
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  • 38
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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 dependence of the molecular electrostatic potential V on the method of calculating the wave function and on the basis set has been examined for three electronic states of H2CO. The calculations analyzed here refer to two different basis sets: a minimal set and a split-valence shell set, both supplemented with diffuse p orbitals. The methods of calculation include the SCF procedure (for the ground state), CI procedures of increasing complexity, which practically reach their asymptotic limits, and, for the excited states, simpler methods (rigid orbital excitation, complete CI of single excitations, electron-hole potential methods). It appears that in the ground state the two bases give equivalent descriptions of V when the CI process reaches the asymptotic limit and that the SCF descriptions approximate fairly well the more accurate ones. For the 3A1(π → π*) state the conclusions on the two basis sets are similar and, in addition, it is shown that a simple method (EHP) gives an approximation of V that reproduces the essential features of the complete CI calculations. The inadequacy of both basis sets for the representation of the 1A1(π → π*) state turns out to be evident. A discussion is presented concerning the possibility of adopting the calculation of V as an auxiliary tool to compare the accuracy of different descriptions of the same electronic state.
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  • 39
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    International Journal of Quantum Chemistry 13 (1978), S. 597-603 
    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 multiple scattering method is used for determining the total cross section of elastic electron scattering for the SF6 molecule in the energy range 10-60 eV.
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  • 40
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    International Journal of Quantum Chemistry 13 (1978), S. 627-634 
    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 approximate way of calculating the supermolecular density applied in the Gordon and Kim method is examined. If the supermolecular density is approximated by a sum of the subsystem densities, the results for the individual contributions to the interaction energy (kinetic, potential) appear to be incorrect as compared with those obtained in the SCF approach and in first-order perturbation theory. However, a considerable improvement of the statistical results is obtained if a more suitably calculated supermolecular density is used. All calculations have been carried out for the He2 system.
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  • 41
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    International Journal of Quantum Chemistry 13 (1978), S. 693-695 
    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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  • 42
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    International Journal of Quantum Chemistry 13 (1978), S. 719-730 
    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 survey of our recent work on algebraic structures and reduced-density-matrix theory is presented. Our approach leads to a method of classifying reduced density matrices and generalizes the notion of open and closed shells in many-body theory.
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  • 43
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    International Journal of Quantum Chemistry 13 (1978), S. 777-790 
    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: Optimal orbital exponents are approximated by minimization of the reduced Hamiltonian orbital ground state energy. They appear to be as good as and are obtained at much less expense than the values derived by the usual SCF exponent optimization scheme. Partitioning of energy into 0-energy, 1-energy, and 2-energy (Absar and Coleman, Int. J. Quant. Chem. 10, 319 (1976); Chem. Phys. Lett. 39, 60 (1976)) is used to study the variation in the electronic energy surface upon variation of orbital exponents. The 1-energy operator, the natural orbitals of which are the reduced Hamiltonian orbitals, is compared with the SCF operator.
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  • 44
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    International Journal of Quantum Chemistry 13 (1978), S. 791-799 
    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: Representable reference density matrices are applied to the graphical description of the Coulomb hole in a CI wave function for the first excited 1S state of the four-electron boron ion B+. It is found that a satisfactory picture of the Coulomb hole emerges only when the symmetry of the correlated wave function is recognized in the construction of the reference full-density matrix.
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  • 45
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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: Ab initio LCAO SCF MO calculations are carried out on planar Co-porphine with a basis set of roughly double zeta quality for Co and N and of single zeta quality for C and H. The net charge on Co and N and the overlap population between them are 1.78, -0.57, and 0.06, respectively, in the 2A1g, state, which is known to be the ground state by experiment. The bonding in this complex is thus largely ionic. The first and second calculated ionization potentials are 6.51 and 6.77 eV, respectively, and are in reasonable agreement with the observed ionization potentials of 6.44 and 6.62 eV for Ni-tetraphenylporphine. CI calculations within the framework of the ligand field theory are also performed. The calculated order of the five lowest states is 4B2g ≈ 4Eg, 4A2g, 2A1g, 4Eg from below and is not in agreement with the semiempirical order of 2A1g ≈ 4B2G, 4A2g, 2Eg, 4Eg determined by Lin.
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  • 46
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    International Journal of Quantum Chemistry 11 (1977), S. 1005-1015 
    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 explored two areas of approximately rigorous calculations for computing nonempirical wave functions for heavy and/or large molecules orders of magnitude faster than with conventional ab-initio methods but with the same chemical accuracy.First, we have developed and used a series of programs (starting from our new fast sets of ab-initio Gaussian SCF and SCF-CI programs) incorporating ab-initio effective core model potentials (MOD-POT) which allow one to treat only the valence electrons explicitly, plus a charge conserving integral prescreening, which cuts down significantly on the number of integrals that have to be calculated, stored, or processed for a large molecule. We have named this latter procedure VRDDO (variable retention of diatomic differential overlap). With these MODPOT and MODPOT/VRDDO methods we have explored a variety of small, medium, and large systems ranging from electron affinities of atoms through to molecules of biological interest and large boron hydrides. The results compared to ab-initio SCF or SCF/CI calcuations are very good, usually within 0.001 to 0.002 a.u. for orbital energies and gross atomic populations (GAPS) and even better along potential energy curves.Secondly, we have explored the use of the MS-Xα method for less conventional molecules and properties than those for which it is customarily employed.
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  • 47
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    International Journal of Quantum Chemistry 12 (1977), S. 11-17 
    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 AMO function of the hydrogen molecule ψ = ψc + η ψi, where ψc is the covalent part and ψi the ionic part, is investigated for small internuclear distances R. We found η → -1 as R →,-1 as R → 0, contrary to the intuitively expected limit η → 1. However, near R = 0 an analytical expression of ψ is derived, showing that ψ reduces to the helium ground state as R → 0. We have proved that the empirical concept „covalent and ionic character“ should be replaced by the symmetry argument in the case of small R.
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  • 48
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    International Journal of Quantum Chemistry 14 (1978), S. 191-207 
    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 properties of biorthonormal sets and their use in quantum chemistry are discussed. A theoretical description of the interaction between one-electron atoms is presented. The description is based on a single orbital per electron but is otherwise complete. Structurally simple relations are derived for the energy of interaction, and theoretical justifications for the London equation and the diatomics-in-molecules method are presented. Some comments on the stability of spin-coupling-optimized methods are made.
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    International Journal of Quantum Chemistry 14 (1978), S. 181-190 
    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 SCF method using localized molecular orbitals which are built up on hybrid atomic orbitals is proposed to obtain the charges in infinite crystals. Hybrid orbitals are built up on a minimal STO basis set. The formalism has been adapted in order to take into account the periodicity of the system and its infinite size by introducing the Madelung constant. The total energy is given by an infinite sum of terms each corresponding to the energy of a bond in the crystal field. Minimizing this bond energy with respect to eigenvectors it is straightforward to obtain the electronic charges, whence the polarity, i.e., the ionicity, of bonds. In this first paper, we study and discuss the polarity of bonds in zincblende and wurtzite-type compounds built up on first and second row elements. Our values are coherent between themselves and in agreement with other authors' results. The connection with electronegativity and polarizability is discussed.
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    International Journal of Quantum Chemistry 14 (1978), S. 231-237 
    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 to improve trial wave functions is given in terms of the off-diagonal hypervirial theorem. This procedure is closely related to the optimum scaling method which is valid for the diagonal hypervirial theorem. The second excited state of the one-dimensional oscillator model is employed as an example, and improved wave functions and expectation values are calculated. The results are compared with previous values based on the diagonal hypervirial theorem.
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    International Journal of Quantum Chemistry 14 (1978), S. 289-297 
    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: In this paper, MC-SCF and CI methods have been explored for the calculation of ground- and excited-state energies of some aromatic heterocycles in the PPP framework. A new algorithm for solving the orbital equations in MC-SCF theory has been suggested and its performance has been compared with the conventional gradient optimization technique. Energies of first few transitions have been calculated and compared with rather extensive CI results.
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    International Journal of Quantum Chemistry 14 (1978), S. 319-327 
    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 analytical potential function for the pairwise interaction of methane and water is reported. The function is representative of 225 ab initio quantum-mechanical calculations of the intermolecular interaction using 6-31G self-consistent-field molecular-orbital theory. The statistical parameters of the curve fitting are given and isoenergy contour maps of the interaction energy are presented and discussed.
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    International Journal of Quantum Chemistry 14 (1978), S. 341-341 
    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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    International Journal of Quantum Chemistry 14 (1978), S. 353-359 
    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 review the methods and some applications of complex scaling transformation as well as some goals that now seem accessible using this technique in atomic and molecular physics.
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    International Journal of Quantum Chemistry 14 (1978), S. 393-418 
    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 theories of the dilatation, r → r eiθ, and translation, x → x + iq, transformations as related to the Stark problem are reviewed, and new results obtained. Results for the hydrogen atom n = 1 and n = 2 levels and the 1P0, 2s2p H- shape resonance in dc fields are presented, and the extension to the ac Stark effect made. Spectral estimates are made using the technique of the numerical range and via discussion of several model problems, using both coordinate rotation and coordinate translation.
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    International Journal of Quantum Chemistry 14 (1978), S. 457-513 
    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 theory of this paper deals with certain aspects of the formal properties of atomic and molecular highly excited nonstationary states and the problem of calculating their wave functions, energies, and widths. The conceptual framework is a decay theory based on the consistent definition and calculation of the t = 0 localized state, |Ψ. Given this framework, the following topics are treated: (a) The variational calculation of Ψ0 and E0 using a previously published theory that generalized the projection operator approach to many-electron systems. (b) The exact definition of the resonance energy. (c) The possibility of bound states in the continuum. (d) The relation of Ψ0 to the resonance (Gamow) function Ψ and of the Hamiltonian to the rotated Hamiltonian H(θ) based on the notion of perturbation of boundary conditions in the asymptotic region. (e) The variational calculation of real and complex energies employing matrix elements of H and H2 with square-integrable and resonance functions. (f) The mathematical structure of the time evolution of |Ψ0〉 and the possibility of observing nonexponential decays in certain autoionizing states that are very close to the ionization threshold. (g) A many-body theory of atomic and molecular resonances that employs the coordinate rotation method.
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    International Journal of Quantum Chemistry 14 (1978), S. 623-634 
    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 theoretical justification of the model potential method is studied in some detail. The correct equations within the framework of Roothaan's open-shell scheme are derived and the approximations necessary to get a workable method are discussed. Analysis of the local part of the model potential suggests a new analytical form for it. The new expression is theoretically more consistent than the original one, and it can be determined in a more straightforward way. A basis set approximation, which is particularly suitable for approximate evaluation of two-electron integrals when only valence orbitals are involved, is discussed and tested with encouraging results. The ideas are tested on the Fe and I atoms.
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    International Journal of Quantum Chemistry 14 (1978), S. 649-657 
    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 polarization model, originally developed to describe deformable and ionizable water molecules, has been extended to hydrogen fluoride. Since electronic polarization is explicitly included, the interaction energy in aggregates of molecules (with or without ions) is nonadditive. The model properly describes the structure of (HF)2, including off-axis bending of the proton acceptor molecule. Calculations are presented to illustrate elementary gas-phase reactions involving proton transfer between HF and F-, and H2F+ and F-.
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    International Journal of Quantum Chemistry 14 (1978), S. 635-639 
    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 concept of a universal basis set for electronic structure calculation is illustrated by presenting results obtained when basis sets are transferred from one atom to another. A single Slater-orbital basis set, consisting of nine 1s and six 2p functions, produces Hartree-Fock total energies and orbital energies in good agreement with the most accurate calculations of these energies obtained using different basis sets individually optimized for each atom. Transferability of integrals is a natural consequence of the use of the same basis set for each atom in a molecule.
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    International Journal of Quantum Chemistry 14 (1978), S. 641-648 
    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 possible uses of the half-projected Hartree-Fock (HPHF) scheme for computing potential-energy surfaces for both singlet and triplet states are investigated. For that purpose, a new procedure based on the simultaneous solution of two eigenvalue equations is presented for calculating the HPHF function. Applications are given in the cases of the singlet ground state and lowest triplet state of the lithium molecule. In both cases, the HPHF scheme is found to yield the correct general shape of the curves. The features of these curves are discussed. Finally, it is concluded that the HPHF model seems to be useful as a tool for determining potential-energy surfaces, especially in the cases of large molecules where more sophisticated methods are unmanageable.
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    International Journal of Quantum Chemistry 14 (1978), S. 737-740 
    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 molecular spectra of formamide (HCONH2) are interpreted by the use of the new semiempirical method HAM/3. Very good agreement with experiments can be obtained for the calculation of all valence ionization energies as well as for the (negative) electron affinity. In addition, the calculated excitation energies allow an unambiguous interpretation of the UV spectrum, for which previously different ordering of the triplet 3ππ* and 3nπ* transitions have been suggested.
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    International Journal of Quantum Chemistry 15 (1979) 
    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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    International Journal of Quantum Chemistry 15 (1979), S. 121-129 
    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 molecular electrostatic potentials computed by the overlap-multipole-expansion procedure (OMTP) are compared to exact electrostatic potentials computed with the same Gaussian basis set, for different molecular species. It is shown that at distances of the molecule larger than 2.2 Å, the OMTP values compared to those of the exact ones are within an error of 0.5 kcal/mol. This error decreases with increasing distance. For distances below this limit the OMTP potentials may be used as a first indication of the trends of the molecule, provided the values to compare are not too close.
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    International Journal of Quantum Chemistry 15 (1979), S. 109-120 
    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 random-walk method of solving the Schrödinger equation is applied to the 1B1g and 1B2g states of the H4 square with side length 2.4 a.u. The results provide an independent check of the accuracy of prior variational calculations for these states. With node structures for the 1B1g state taken from a variational calculation with a single-zeta basis set and taken in the simplest form meeting symmetry requirements, the calculated energies are lower than the expectation value of the energy for the single-zeta basis set but not as low as the expectation value for an optimized-exponent double-zeta basis set with polarization terms. Comparisons of results give no suggestion of a barrier height lower than ∼120 kcal/mol for passage through the square configuration in the exchange reaction H2 + D2 → 2HD. For the 1B2g state with node structure in the simplest form meeting symmetry requirements the calculated energy is ∼65 kcal/mol lower than the expectation value of the energy for variational calculations with a double-zeta basis set.
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    International Journal of Quantum Chemistry 15 (1979), S. 135-145 
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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: Two distinct approaches to the calculation of first-order properties with a limited CI wave function are discussed. One is based on the Hellmann-Feynman theorem and the other on the direct evaluation of the total energy derivative at zero perturbation. Corrections to the Hellmann-Feynman expectation value are given for the CI wave function consisting of a single determinant reference state and all single and double replacements of this. These corrections are the extended Brillouin matrix elements and involve interactions between the zeroth-order wave function and triply substituted configurations. The usefulness of these matrix elements for the generation of MC SCF orbitals and for the calculation of cluster corrections to the wave function is briefly discussed. The formulas for the Brillouin matrix elements expressed in terms of one- and two-electron integrals have been automatically generated using the syntax of the algebraic program SCHOONSCHIP.
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    International Journal of Quantum Chemistry 15 (1979) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 15 (1979), S. 207-242 
    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 argue that the goal of developing a satisfactory general formalism for the justification of effective π-electron Hamiltonians, as well as for ab initio calculation of their parameters (α, β, and γ), has now been achieved. The need for a fully linked many-body formalism is emphasized; this feature requires a Rayleigh-Schrödinger (RS) type of degenerate perturbation theory. A number of apparently different degenerate RS perturbation formalisms are reviewed. Most of these formalisms are actually identical term-by-term, when their RS expansions are worked out explicitly; the formal relations that prove their complete equivalence are presented and discussed. One of these formalisms, a version developed by the author for related open-shell problems in nuclear physics, is shown to be most convenient for many-body applications. This is owing to the relatively simple and transparent nature of its general algebraic structure, which facilitates partial summation to infinite order. A simple and concise derivation is presented for the algebraic features of this preferred formalism, and its many-body (linked cluster) aspects are briefly discussed. The recent development of a nonperturbative (coupled-cluster) analog of this formalism is also described. Some practical issues are examined, including the choice of orbital basis. Illustrative numerical results are presented, based on the calculations of Iwata and Freed. Several remaining problems are described; these are both qualitative and quantitative in nature, and their resolution will require some detailed calculations.
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    International Journal of Quantum Chemistry 15 (1979), S. 359-359 
    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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  • 69
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    International Journal of Quantum Chemistry 15 (1979), S. 389-401 
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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: It is found that ordinary STOs fall off too fast in the atomic region in many cases. A new type of basis set, which is more adaptable to the rather different requirements of the various atomic orbitals in an atom, is developed. The suggested functional form χ(r) = Nrn-1 exp{-α[(βr + 1)1/2 - 1]} contains the STOs as a limiting case. Calculations on a series of atoms from H to Zn show that the new basis gives better results than STOs for equal basis set size. The necessary integrals do not present any problem to evaluate.
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    International Journal of Quantum Chemistry 15 (1979), S. 403-410 
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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 valence spectrum of CoO has been calculated using the CoO610- cluster, stabilized by an electrostatic field, as a model of bulk CoO. The wave functions were generated using basis sets of better than double-zeta quality. SCF wave functions were obtained for the ground state and for the first ionized state of the cluster. Limited CI calculations were performed using these orbital sets. The lowest states of the ion correspond to the main lines in the spectrum, while higher states can give rise to high-energy satellites to the main lines. The relative intensities of these satellites were estimated in the case of high-energy incident photons.
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  • 71
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    International Journal of Quantum Chemistry 15 (1979), S. 445-445 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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  • 72
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    International Journal of Quantum Chemistry 15 (1979), S. 411-421 
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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: Pseudospectra from Gaussian basis set calculations within a frozen-core approximation have been used in a moment analysis to obtain Tchebychev profiles for the photoabsorption process in the valence shell of Ne. The profiles show good agreement with cross sections obtained in equivalent calculations using numerical atomic wave functions and continuum orbitals, particularly when the dipole-velocity form is employed. Variation of the basis sets shows that it is possible to obtain meaningful photoabsorption profiles using 13-15 virtual orbitals to describe the outgoing electron.
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  • 73
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    International Journal of Quantum Chemistry 15 (1979), S. 481-489 
    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 paper reports the study of a possible mechanism of Ca+2 activation of prostaglandin PGF2α on the basis of molecular-orbital and conformation-energy calculations. The electronic charges on various atoms of the molecule have been evaluated from the available crystallographic data by the extended Hückel theory (EHT). Conformation energies were calculated for intrinsic torsional rotations around the C11—C12, C7—C8, and C14—C15 bonds. The minimum energy conformation was found to differ from the crystallographic conformation by 9.3 kcal/mol. Some additional local energy minima are also reported within this range. The calculation of the long-range interchain interaction energy between the α and ω chains shows variation with conformation. The binding site for the Ca+2 ion has been estimated on the basis of the molecular electrostatic potentials. Such a binding site was found near the carboxyl group, which agrees with the current chemical thinking. Changes in the electronic charge distribution due to Ca+2 complexation were studied by EHT method using the supramolecular approach. Calcium complexation decreases the conformation energy by 2-3 kcal/mol and has a small effect on the interchain interaction energy.
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  • 74
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    International Journal of Quantum Chemistry 15 (1979), S. 491-497 
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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: Several analogs of valinomycin have been simulated. These are analogs obtained by changing the configuration of the amino acid and hydroxy acid residues one at a time. Nonbonded interactions have been calculated for three conformations of each analog. The electrostatic and polarization contributions to the energy are conformation selective, whereas the Pauli repulsion is the only component which is isomer selective. For the ring chirality considered here the analog of valinomycin having all the three L-valyl residues replaced by D-valyl residues is predicted to be frozen in a “top open” conformation.
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  • 75
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    International Journal of Quantum Chemistry 15 (1979), S. 499-510 
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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 ab initio SCF LCAO-MO method is used to compute the main electronic properties of a purine nucleoside, adenosine, in two specific conformational arrangements (3′-endo conformation of the ribose, gt orientation of the extracyclic CH2OH group, anti orientation of the base with respect to the sugar and 3′-endo conformation of the ribose, gg orientation of the extra-cyclic CH2OH group, syn orientation of the base with respect to the sugar). The results are compared with those performed for the isolated component fragments, adenine and 3′-endo riboses.
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  • 76
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    International Journal of Quantum Chemistry 15 (1979) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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  • 77
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    International Journal of Quantum Chemistry 15 (1979), S. 547-557 
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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 cyanide-isocyanide isomerization has been studied with ab initio calculations in an STO-3G basis as applied to NCNCO, NCCNO, NCOCN, and NCONC, and the corresponding isocyanides. Geometry optimization has been performed on these cyanides, their isocyanides, and their hypothetical transition states. The energies of isomerization were calculated to be 42.2, 29.8, 44.6, and 41.4 kcal/mol, respectively, while the energy barriers were found as 84.3, 67.5, 107.9, and 106.8 kcal/mol. Overlap populations and atomic charges were employed to provide simple correlations of the results.
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  • 78
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    Topics: Chemistry and Pharmacology
    Notes: Configuration-interaction calculations, with an extended basis, are carried out on the ground and lower excited states of O2 and O2+ at and near the equilibrium internuclear distance (R = 2.3 a.u.) of the ground state of O2. Particular attention has been paid to the two lowest 3Σu- states, and the mixing of the valence and Rydberg characters in these states are studied. The lowest 3Σu- state is a Rydberg-type state for R 〈 2.3 a.u., but becomes valence-type for R ≳ 2.3 a.u. The second 3Σu- state, which is 1.6 eV above the lowest 3Σu- at R = 2.3 a.u., changes its character from Rydberg to valence, valence to Rydberg, and then to valence again when R increases from 1.9 to 3.1 a.u. Satisfactory agreement between the calculated and experimental vertical excitation energies is obtained.
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  • 79
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    International Journal of Quantum Chemistry 15 (1979), S. 559-566 
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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 new form of pseudopotential for applicaiton in ab initio molecular calculations is described. A method for determining pseudopotential parameters is suggested and pseudopotential parameters of double-zeta quality are presented for the first row atoms of the periodic table. The pseudopotential is especially well suited for incorporation into the floating-spherical-Gaussian-orbital (FSGO) method, though it is not restricted to any particular method. Applications of the resulting pseudo-FSGO method to BeH2, BH3, CH4, and C2H6 are presented.
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    International Journal of Quantum Chemistry 15 (1979), S. 567-578 
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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: Pseudopotential theory is introduced into the ab initio FSGO molecular fragment method. A theoretical background for the pseudopotential fragment description and a method for large molecule formation is presented. Core-valence electron separation is achieved at both levels of the calculations with the resulting simplification of the molecular calculations. Using pseudopotentials of double-zeta quality a detailed description of pseudopotential molecular fragments CH4 (tetrahedral) and CH3 (planar) is presented. Applications of the pseudo-FSGO molecular fragment method to hydrocaroons are discussed. The results are compared to those of the original FSGO method and experiment.
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    International Journal of Quantum Chemistry 15 (1979), S. 579-588 
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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 procedure is outlined for a programmable spin-free configuration-interaction (CI) study in molecules using single-parameter alternant molecular orbitals for generating various configurations. The configurations were chosen to form bases for the irreducible representation {2N/2-2, 12S} of the general linear group GL(n). Using a transformation to biorthogonal space the CI matrix elements of a spin-free Hamiltonian were generated. The procedure has been used to obtain the π-electron energies for the 3,1Ag and 3,1Bu states of cis- and trans-butadiene.
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    International Journal of Quantum Chemistry 15 (1979), S. 713-715 
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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 Longuet-Higgins group is used to obtain an alternative formulation of a criterion for optical activity of nonrigid molecules recently given by Frei and Günthard.
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    International Journal of Quantum Chemistry 16 (1979), S. 5-17 
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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 properties of exciton and soliton excitations in one-dimensional molecular systems and in α-helical protein molecules are investigated. It is shown that collective excitations - solitons, corresponding to a combination of vibrational excitations in peptide groups and a local deformation of molecules - are possible in α-helical protein molecules. These excitations move along the molecule without energy losses and are perfect energy carriers. A qualitative description of the shortening in the length of muscular fibers is given using the concept of solitons occurring under the hydrolysis of ATP molecules at the ends of thick fibers contained in the sarcomeres of muscular fibers.
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    International Journal of Quantum Chemistry 16 (1979), S. 31-42 
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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 new electron structural mechanism is proposed for interpretations in molecular biology, in addition to the already existing theories of Szent-Györgyi (semiconductivity) and Fröhlich (long-range coherence). The hypothetical “intermediate-” or “zigzag states” (ZZS) of solids are investigated by the recursion (transfer matrix) method. The physical reality of the ZZS is discussed up to an SCF DODS-type theory and the necessity of additional less approximate investigations is emphasized. The possible role of ZZS in the explanation of: (i) translation in protein synthesis, (ii) energy and charge transfer processes, as well as (iii) initiation of protein formation is outlined.
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    International Journal of Quantum Chemistry 16 (1979), S. 19-29 
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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: Preferred conformations of phospholipids have been predicted through quantum-chemical techniques and classical potential functions. An essential condition for a conformation to exist in a biomembrane is that it should be possible for it to organize in the form of a bilayer. Taking into consideration the conformational flexibility of the polar head group, organization at the lipid-water interface has been considered. The biological implications of such an organization in terms of formation of “hydrophobic channels” is discussed. Quantum-mechanical investigations on the transport phenomenon have shown that the “selectivity” of biological membranes is connected with the “organization.” Calculations of the quantum-mechanical transmission coefficients for different model potential profiles indicate that minor differences in the height of potential barriers in certain regions can lead to significant changes in transmission coefficients. The “directional selectivity” of substrates (differences in transmission coefficients for flow in and out of the cell) can be explained on the basis of differences in membrane organization. These results have some important consequences in the evolutionary process in biological membranes.
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    International Journal of Quantum Chemistry 16 (1979), S. 43-50 
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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: In the myosin-auramine O system 10 or 11 binding sites of auramine O on the rod-like part of myosin were discovered. The myosin fluorescence decreases with an increase in auramine O concentration. This is evidence of the excitation energy transfer from tryptophanyls situated near the binding sites to auramine O. The effective distance of energy transfer is 35 Å. It is suggested that the light meromyosin has binding sites with periodicities of 77-86 Å. Every binding site has a negative charge and hydrophobic locus.
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    International Journal of Quantum Chemistry 16 (1979), S. 51-56 
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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 transition from quantum chemistry to quantum biology is discussed, and the contributions that quantum biology can make to the study of biological structure and process are outlined. The need for extensions to the theory to deal with larger systems, to include solvent effects and to account for specificity, are emphasized.
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    International Journal of Quantum Chemistry 16 (1979), S. 57-64 
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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: Pseudopotential theory is introduced into the ab initio FSGO molecular fragment method. Pseudopotential molecular fragments using pseudopotentials of double-zeta quality are characterized, and a method of their assembly into larger molecules is presented. Core-valence electron separation is achieved at both levels of the molecular calculations. Heteroatom incorporation into the method is also considered. Applications of the pseudo-FSGO molecular fragment method to hydrocarbons and simple molecular systems containing heteroatoms are discussed. Results are compared to those of the original FSGO method and experiment.
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    International Journal of Quantum Chemistry 16 (1979), S. 65-70 
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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: Pair energies contributing to the correlation energies of the outer-shell electrons (n = 3) as well as for the 1s2 and 2s2 pairs are computed for the Zn2+ closed-shell ion by means of the variational-perturbation method starting with the sum of one-electron Hartree-Fock operators as the zeroth-order Hamiltonian. The results allow an understanding of the electron correlation for pairs of electrons of the p and d type. For 3p3d pairs it has been found that the correlation energy for the singlet pair of 1D symmetry is lower than for the triplet pair 3D. The 3l-3l′ correlation energies are compared with the MBPT results of Kelly and Ron for Fe. The total correlation energy of the outer shell is -1.032 a. u.
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    International Journal of Quantum Chemistry 16 (1979), S. 71-77 
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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 intermolecular electronic correlation contributions to the Coulomb component of the nucleic acid base interaction energy are estimated. The Coulomb energy is evaluated with the use of atomic monopoles, which are determined from the π-electronic densities calculated by the SCF method and by employing partially or completely optimized APSG wave functions. When the correlation is thus taken into account, a systematic decrease in atomic charges occurs; this effect is considerable only if an optimized orbital set is used. As a result, the Coulomb interaction energy due to the π-electronic atoms decreases from -1.13 to -0.85 kcal/mol for the AT pair and from -7.15 to -4.61 kcal/mol for the GC pair.
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    International Journal of Quantum Chemistry 16 (1979), S. 79-86 
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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 for processing the enthalpy, entropy, and Gibbs free energy terms of formation of the individual isomers of n-particle clusters obtained by means of quantum-chemical calculations, to enable a comparison of these partial theoretical characteristics with the overall experimental ones. The general scheme of weighting treatment is illustrated by examples based on recent quantum-chemical results of studies of isomeric forms of (NO)2, (H2O)5 and (D2O)5, and CH3OH · 3H2O and CH3OH · 6H2O clusters.
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    International Journal of Quantum Chemistry 16 (1979), S. 87-110 
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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 electronic structure of a series of 25 chlorinated dibenzo-p-dioxins and dibenzofurans has been characterized by means of the ab initio molecular fragment technique. This information has been employed to investigate some of the factors affecting the affinity of the molecules for the hepatic cytosol binding species described by Poland, Glover, and Kende. A quantitative structure-activity relationship involving electronic and steric parameters could be established from the data. It appears that the toxins act as electron acceptors in a charge-transfer complex with the receptor.
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    International Journal of Quantum Chemistry 16 (1979), S. 111-117 
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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 circular dichroism of molecules, which are large compared to the wavelength of light, is considered. Explicit expressions are obtained for the circular dichroism and absorption of an exciton dimer and of a free particle on a helix. The dimensions are described for which the dipole approximation for the optical properties fails.
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    International Journal of Quantum Chemistry 16 (1979), S. 133-152 
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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 analysis of modern physical mechanisms of electron transfer in proteins is given. The tunnel electron transfer and donor-acceptor electron transfer through conducting states of a protein chain are discussed in detail. The expressions for the values of the electron resonance interaction and the formulas for probabilities of electron transfer between vibronic levels of donor and acceptor states in the presence of “transverse” and “longitudinal” relaxation are given.
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    International Journal of Quantum Chemistry 16 (1979), S. 119-132 
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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 expressions for the polymer absorption band hypochromism and oscillator strength are studied in frames of the first-order perturbation theory. The physically justified approximations for a polymer hypochromism calculation are indicated. The uniform interpretation of the effect origin is given independently on the approximation used. In frames of the perturbation theory the DNA hypochromism formula is obtained, from which the known experimental dependences of hypochromism on chain length and polymer helicity degree follows directly. The analytic expression of the DNA hypochromism dependence on AT pairs content is obtained. It is established that in most cases for natural DNA the nucleotide sequence does not influence in practice the value of the hypochromic effect.
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    International Journal of Quantum Chemistry 16 (1979), S. 153-157 
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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 intramolecular interaction energy of the regular double-helical polynucleotide as a function of variables that determine the mutual position of base pairs and sugar pucker was calculated using atom-atom potentials. The calculations showed the existence of two valley-like regions with minimal values on the energetic surface. One of them corresponds to the A family of nucleic acids, the other to the B family. The points that correspond to the models constructed by means of x-ray data are placed in a conformational space near the lines that describe the position of the bottom of the valleys.
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    International Journal of Quantum Chemistry 16 (1979) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 16 (1979), S. 847-855 
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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 investigation of the factors determining the formation and stability of the higher biopolymers structures is one of the most important trends of the development of molecular biophysics. A feature common to most macromolecular systems under physiological conditions is that they function in an aqueous environment. Thus, it is natural to assume that the peculiarities of biological macromolecules structures and their functional activity as well are closely related to the specific properties of such a unique solvent as water. The investigations of the conformational changes of biopolymer, induced by dehydration of the macromolecule, give information about the nature of the forces stabilizing its structure. The dehydration of the macromolecule in solution can be attained by addition of a nonaqueous cosolvent. Generally low-molecular-weight aliphatic alcohols, amides, and amines are used as a nonaqueous component. At present a vast number of experimental and theoretical data concerning the properties of water and aqueous systems are available. The specificity of water as a solvent arises primarily from the spatial hydrogen-bonded structure. The addition of a nonaqueous component exerts changes in this structure, which evolve to the singularities of the physical characteristics of water-nonelectrolyte mixtures. It is generally assumed that nonelectrolytes may be divided, according to their effect on the spatial water structure, largely into two basic classes: (1) the structure makers, i.e., the compounds of aliphatic alcohols type; (2) the structure breakers, i.e., the compounds of urea type. The agents belonging to the first class show a stabilizing effect in the range of low nonelectrolyte content. At a certain critical concentration, Ccrit, characteristic of each substance, the nonaqueous solute molecules leave the cavities of the spatial water structure which leads to a disruption of the latter. The agents belonging to the second class exert a structure-breaking effect even in the range of extremely low concentrations, which arises from their high competitive ability for hydrogen bonding.
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    International Journal of Quantum Chemistry 16 (1979), S. 877-882 
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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 physical aspects of the primary charge separation processes in bacterial photosynthesis are discussed. The donor-acceptor model of electron transfer due to participation of protein current states is used. The kinetics of photosynthetic reaction center (PRC) processes is investigated and the PRC energetic scheme is constructed using the nonequilibrium density matrix method. It is shown that with allowance for the effect of vibrational sublevels of states participating in transitions the theory describes well experimental data.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 100
    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: This paper analyzes the low-temperature magnetic circular dichroism of NO-Fe(II)hemoproteins in detail. We include the Jahn-Teller effect in our consideration of the low-temperature MCD results.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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