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  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 489-492 
    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 for the evaluation of the Fourier transform of two-center functions is presented.
    Type of Medium: Electronic Resource
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  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 513-521 
    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 translation is made of spin projection methods into the language of second quantization. This leads to a new formula for the Sanibel coefficients and expressions convenient to use for automatic calculation of spin projections.
    Type of Medium: Electronic Resource
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  • 103
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 537-551 
    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 of evaluating the long range terms (electrostatic, polarization, dispersion) of the interaction energy between molecules at intermediate distances (i.e. distances of the order of magnitude of the molecular dimensions) is considered. Instead of being approximated by its dipole part, the exact interaction Hamiltonian is treated as proposed by Longuet-Higgins [11], i.e. the matrix elements are interpreted as electrostatic interactions between state and transition charge distributions. These charge distributions are approximated in a systematic way by sets of point charges (localized on the atoms) or sets of dipoles (localized on the bonds). The various contributions to the energy may then be expressed in terms of atomic net charges and bond polarizabilities. More refined approximations of the charge distributions could be used and correspondingly improved formulae could be derived: as an example, a formula for the σ-π dispersion energy is derived, where the σ charge distributions are approximated by bond transition dipoles (leading to σ bond polarizabilities in the final formula) while the π charge distributions are approximated by atomic charges.
    Type of Medium: Electronic Resource
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  • 104
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 1061-1064 
    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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  • 105
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 881-887 
    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 ethylene molecule has been investigated by means of the General SCF-MO-LC(LCGO) Program System for 12 different nuclear positions, taking all electrons into account. The equilibrium distances and angles as well as all force constants of the totally symmetric vibrations with the corresponding frequencies have also been calculated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 106
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 983-999 
    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: Semi-empirical calculations of the π-band structure of planar and three-dimensional graphite are described. Special attention is given to the significance of band parameters. The theoretical results are in good agreement with experiment.
    Additional Material: 15 Tab.
    Type of Medium: Electronic Resource
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  • 107
    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: Expressions of the matrix elements of the spin-other-orbit and spin-orbit interactions for the various multiplets of all the states of ƒ2- and ƒ3-electron configurations are reported and used to evaluate the Hartree-Fock values of these interactions in the neutral atoms Ce(4ƒ2), Pr(4ƒ3), Ho(4ƒ11) and Er(4ƒ12). The required values of the spin-spin parameters M(K)s, and the spin-orbit parameter ζ for these atoms were obtained using numerical Hartree-Fock wave functions.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 108
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 1069-1070 
    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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  • 109
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 17-24 
    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: 3 Tab.
    Type of Medium: Electronic Resource
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  • 110
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 25-32 
    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 method of calculating wave functions for an electron-nucleon system by a variational method originally suggested by Born and Oppenheimer [1] is rigorously investigated. As an application we sketch the calculation of a simple nonadiabatic wave function for the system.
    Type of Medium: Electronic Resource
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  • 111
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 246-246 
    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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  • 112
    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: Methyl groups in flavins are best treated by the group-orbital approximation. The pseudo-heteroatom approximation overestimates methyl hyperconjugation with the Pariser-Parr-Pople SCF-MO method. Singlet π → π* transition energies are calculated by various MO methods with differing degrees of sophistication, and the results from the P—P—P method agree reasonably with the experimental values. 2- and 4-thioflavin analogs are also treated satisfactorily. The effects of position and number of the methyl groups on the spectra of flavins are described in detail. Rough estimates of the n → π* energies of flavins suggest that the lowest singlet excited state is (π, π*), consistent with the fluorescence and phosphorescence polarization data.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 113
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 349-370 
    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 convergence radius of the series expansion for the energy of H2+ in the δ-function model (in terms of the perturbation parameter μ/λ, where μ is the charge of the perturbing nucleus and λ the fixed charge of the other nucleus) is investigated. A lower bound of this convergence radius (possibly equal to it) previously defined by Robinson [5] is studied analytically as a function of the internuclear distance R and computed numerically. The results differ strikingly from those previously obtained by Robinson who used a simplified but poorer lower bound: in contrast with this poorer bound, the one studied in the present paper is larger than for I every R, from which fact it may be concluded that, contrary to Robinson's previous result, the series expansion of the energy, in the δ-function model under consideration, still converges when μ = λ for every R.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 114
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 123-130 
    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
    Notes: The first part of this paper gives an introduction of different kinds of atomic associations. Furthermore it will be shown that partial systems of united atoms are not only described by their nuclear-charge number, but additionally by their number of electrons. Both characteristics of a partial system of atomic associations may lead to an apparent multiple-valuedness in the transitions between atomic associations. It is shown that the multiple-valuedness of the atomic associations can be understood and eliminated within the Born-Oppenheimer-approximation, which leads to the concept “energyhypersurface”. An example is given by the system {He, H, H, H}+.
    Additional Material: 2 Ill.
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  • 115
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969) 
    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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  • 116
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 195-204 
    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 a variational principle proposed by Hall [1] is shown to be a minimum principle for coulombic systems. Into this principle it is possible to admit a larger class of trial wave functions than is possible in the conventional variational treatment, including wave functions with discontinuities. It is further shown that the upper bounds given by this treatment are always at least as good as that given by the Rayleigh-Ritz method.The theory is then applied to the hydrogen atom and upper bounds to the energy are calculated for various “cutoff” wave functions. It is usually possible to define an optimum “cut off” distance which minimizes the upper bound.
    Additional Material: 1 Ill.
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  • 117
    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: Polarization tensors are discussed in terms of their intrinsic symmetry group which is a direct product of the point group and the subgroup of the permutation group relevant to the experiment. The study of these latter groups is simplified by use of the isomorphism with certain point groups and permutations of suffixes can be visualized by rotations and reflections of the vertices of various objects in space. The approach unites the previous treatments and provides a means of constructing the bases for the irreducible tensor components. The difficulties introduced by Laplace's equation are explained and the information obtainable from induced birefringence experiments (Kerr and Cotton-Mouton effects) discussed for various systems.
    Additional Material: 13 Tab.
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  • 118
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 247-247 
    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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  • 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: Several classes of functions related to the Gaussian have been used with success as basis sets for the representation of atomic and molecular orbitals.We have compared the representation of a hydrogen 1s orbital by a sum of Gaussian lobe functions with its expansion in eigenfunctions of the three-dimensional isotropic harmonic oscillator. The lobe functions are shown to achieve better expectation values of the energy, with fewer terms. The lobe functions have the further computational advantage of not containing high powers of the radius.It is concluded that the lobe functions are a superior basis set for use in calculations of the electronic structure of atoms and molecules.
    Additional Material: 2 Tab.
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  • 120
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 373-376 
    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 Ill.
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  • 121
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 371-373 
    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 the familiar Temple, Stevenson-Crawford, and Weinstein lower bound formulas for eigenvalues are consequences of a much stronger general lower bound formula and the weak “Eckart criterion” for the overlap of the approximate and true wave functions.
    Additional Material: 1 Ill.
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  • 122
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 397-415 
    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: Two-center one-electron integrals needed in certain molecular correlated wave function calculations, using one-center expansion approximation, have been studied. The form of the basic correlated function used in this study is \documentclass{article}\pagestyle{empty}\begin{document}$$ h(r_{12}) = r_{12}^n e^{ - \zeta r_{12} } $$\end{document} The parent integral is expressed in terms of an angular integral, and an auxiliary radial integral depending upon the variables r1, r2, and r12. Several analytical formulas, and a recursive formula are derived for the auxiliary integral, and other related integrals. All these formulas are given in computationally useful forms. Logical flow charts and FORTRAN programs were constructed for computing the basic integrals discussed in the paper. Numerical values of some integrals, thus obtained, are tabulated for comparisons.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 123
    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 studied the validity of the traditional model of a dimer that has been treated exactly by Merrifield and Fulton and Gouterman, solving the vibronic coupled equations by a numerical method. This model takes into account the modification of the nuclear equilibrium configuration, but it neglects the variation of the force constant when the monomer is electronically excited from the fundamental to a given excited state (the corresponding electronic potentials are both considered as harmonic). We have shown by inspection of the absorption and fluorescence spectra calculated by solving the vibronic equation exactly that the variation force constant cannot be neglected, even if it is weak, particularly in the weak coupling region. The weak, intermediate and strong coupling criteria have been deduced, for the model studied, by examination of the dimeric electronic potential surfaces for different cases of intermolecular interactions.
    Additional Material: 6 Ill.
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  • 124
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 485-487 
    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 emphasized that for the theoretical consideration of many problems of defect centers in crystals (especially of problems which need the correct asymptotic behavior of the wave functions) the semiempirical approach can be effective. As an example the spontaneous radiative time decay of the excited F-center in alkali halides is calculated by using the experimental energies of absorption and emission bands.
    Additional Material: 1 Tab.
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  • 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: Pauling's formulas for the calculation of matrix elements for valence bond functions are derived using a simple substitutional process. The results generalize and simplify the formulas. In particular, the formulas do not depend upon orthogonality of atomic orbitals nor upon the nature of the choice of bond structures (canonical or not). The results are particularly adaptable to automatic computation.
    Additional Material: 1 Ill.
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  • 126
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 593-610 
    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 formalism of the variational theory of the Faraday effect established in the first part of this paper is now applied to the actual computation of the Verdet constant of the hydrogen molecule, of water and of some saturated hydrocarbons. The numerical results have a correct order of magnitude and even, for hydrogen, are rather close to the experimental value.
    Additional Material: 2 Ill.
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  • 127
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 493-501 
    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: Expansions in terms of the spherical coordinates of two particles are given for the interparticle distance and its inverse. The expansions are characterized in that each term is a product of analytical one-variable functions. While it is possible to find acceptable expansions for r12, those obtained for r12-1 exhibit extremely slow convergence, unacceptable for practical use. The same objections must be raised against related expansions of multi-centered molecular integrals.
    Additional Material: 3 Tab.
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  • 128
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969) 
    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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  • 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: This article gives pointwise bounds for the wave functions of one-electron molecular systems.
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  • 130
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 115-121 
    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 wave function of the HeHHe+ molecule has been calculated by means of the GENERAL SCF-MO-LC(LCGO) PROGRAM SYSTEM, taking all four electrons into account. The calculations were carried out for a number of linear equidistant, linear non-equidistant, and bent nuclear arrangements. The minimum energy of -5.7930 a.u. was found for a linear equidistant configuration with a He—H distance of 0.939 Å. The corresponding ionization energy was 37.9 eV. An estimation of the energy of formation of HeHHe+ from HeH+ and He based on SCF-calculations on HeH+ and He gave 7.9 kcal/mole. The frequencies of the normal vibrations were calculated.
    Additional Material: 2 Tab.
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  • 131
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 145-145 
    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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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 169-184 
    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 discuss the properties of one version of the least squares (LS) method for the solution of the Schrödinger equation. These properties are exemplified by a number of calculations on the n1S and n3S states of helium, up to principal quantum number three, which are very much more accurate than previous LS calculations on helium. Particular attention is paid to the convergence properties of the LS procedure and we compare it with the simpler Rayleigh-Ritz (RR) procedure in the case when the RR matrix elements are evaluated numerically over the same quadrature mesh as used in the LS procedure. We conclude that although the LS procedure is capable of high accuracy it has no advantages which would justify its sole use in place of the RR procedure. However, it does have some advantages when used in conjunction with RR, in that it gives an estimate of the numerical accuracy of the RR energies.
    Additional Material: 6 Ill.
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  • 133
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    International Journal of Quantum Chemistry 3 (1969), S. 205-218 
    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 biorbital theory called also “identical geminals theory” is applied to the study of a number of conjugated molecules. All basic integrals are determined by means of the Pariser-Parr-Pople procedure. The biorbital theory reproduces about 40 per cent of the correlation energy of the ground state of the molecule; this number is raised to about 70 per cent for the lowest triplet state. The low lying excited states are well represented from the point of view of transition energy as well as from the point of view of symmetry. The occupation number matrix and the charge-bond order matrix are defined and discussed. The overall chemical description of conjugated molecules produced by the biorbital theory is similar to that produced by other theories of electronic structure of molecules. It is concluded that the biorbital theory provides a description the quality of which is, roughly speaking, about half way between those provided by the SCF-MO and complete CI theories, respectively.
    Additional Material: 10 Tab.
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  • 134
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    International Journal of Quantum Chemistry 3 (1969), S. 246-247 
    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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  • 135
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    International Journal of Quantum Chemistry 3 (1969), S. 851-871 
    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: Potential curves that show the energy dependence of hydrogen bonds between carbonyl and hydroxyl groups on the O—H bond length, on the distance between the molecules, and on the angle between the functional groups have been calculated with the CNDO/2 method. The results are presented for a small model system-formaldehyde/water - and for the dimer of formic acid. Good agreement is obtained with the available experimental data. The influence of the molecular geometry on the calculated results is discussed.
    Additional Material: 14 Ill.
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  • 136
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    International Journal of Quantum Chemistry 3 (1969), S. 889-891 
    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: 2-butene has been investigated for different nuclear positions taking all 32 electrons into account, using the SCF-MO-LC(LCGO) method. The calculations show that the energy of the trans-form is 1.1 kcal/mol lower than that of the cis-form. The potential curve between these two forms is shown graphically. The ionization energy was estimated to be 9.0 eV.
    Additional Material: 1 Ill.
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  • 137
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    International Journal of Quantum Chemistry 3 (1969), S. 969-981 
    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 review is given of the current status of our work on electron transport properties and Fermi surfaces in simple metals. A simple classical model is proposed to extend existing theory to account for the effects of electron-impurity interactions on the behavior of magnetoacoustic absorption and the size and shape of the Fermi surface in the alkali metal potassium. The theoretical prediction is compared with measurements of the magnetoacoustic absorptionand Fermi surface diameters in potassium crystals of different impurity levels. An attempt is made to explain, on the basis of the theory of electron-impurity interactions, the decrease by 9% in the Fermi diameter and the departure by 53% in the phase factors of the impure potassium crystal. The results are compared with observations on a zone refined potassium crystal which satisfies the nearly-free-electron model.
    Additional Material: 3 Ill.
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  • 138
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    International Journal of Quantum Chemistry 3 (1969), S. 945-968 
    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 long-range interaction energies for different dissociation products of the HeH+ molecule have been calculated using the Rayleigh-Schrödinger perturbation theory up to the third order in the energy. The calculations were carried out for the ground state (He(ls2) + H+), the first excited state (H(ls) + He+(ls)) and the second excited state Π(H(2pπ) + He+(ls)). The unperturbed states correspond to the dissociation products denoted in parentheses. Assuming the overlap to be zero, expanding the interaction potential in the inverse powers of the internuclear distance R and using the familiarly known perturbation-variational technique, the coefficients of various powers of R-1 in the energy expansion were evaluated. They correspond to different multipole-multipole interactions. The potential energy curves of all three states under consideration were calculated for large values of R. Also calculated were the multipole polarizabilities of the hydrogen atom in the is and 2pπ states and of the helium atom in the ground state.
    Additional Material: 4 Ill.
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  • 139
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    International Journal of Quantum Chemistry 3 (1969), S. 1027-1043 
    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
    Notes: The wave function defining a quantum-mechanical system is considered as the Laplace transform of some distribution and the consequent form of the Variational Principle derived; an integral equation defines the eigenfunctions of a certain subclass. The model of the hydrogen-like atom is used to test the theory; the eigenfunctions and associated energy levels of the ground and excited states are obtained for arbitrary values of the orbital quantum number.
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  • 140
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    International Journal of Quantum Chemistry 3 (1969), S. 569-580 
    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: Vibronic coupling theory is used to construct the vibronic absorption spectrum of the ethylene dimer. It is shown that in this case an extended four-parameter form of the vibronic Hamiltonian should be considered. In addition to the commonly used three vibronic parameters, the difference between the ground and excited state force constants of the monomer is taken into account.Numerical calculations were performed for the dimer geometry resembling that of norbornadiene. Some comments on the interpretation of the absorption spectrum of norbornadiene are made.
    Additional Material: 2 Ill.
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  • 141
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    International Journal of Quantum Chemistry 3 (1969), S. 611-619 
    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: Using a three dimensional free-electron model for the π-electron system the energies of the various singly and doubly excited configurations of benzene have been calculated. It has been found that the energies of the various singly excited configurations are in good agreement with the values obtained by Craig; whereas the energies of the doubly excited configurations are higher than those obtained by Craig. Therefore the configurational mixing for the doubly excited configurations is not necessary in this kind of model.
    Additional Material: 4 Tab.
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  • 142
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    International Journal of Quantum Chemistry 3 (1969), S. 663-681 
    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 full rotational symmetry of the hydrogen atom is lowered to that of the double group of Oh. This is done by a cubic field of electric dipoles. Symmetry-adapted spin orbitals have been calculated and with them the energies of the lowest states as functions of the distance from the dipoles to the atom, the dipole moment, and the size of the atoms forming the dipoles. The Hamiltonian used is obtained by starting with the Dirac equations and then making some simplifications and approximations.
    Additional Material: 10 Ill.
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  • 143
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    International Journal of Quantum Chemistry 3 (1969), S. 723-730 
    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: Energy relations are derived for neutral atoms and isoelectronic sequences. It is shown that the field of the electrons at the position of the nucleus follows a very simple law and the diamagnetic shielding constant may be given in simple analytic form as a function of the atomic number.
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  • 144
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    International Journal of Quantum Chemistry 3 (1969), S. 751-751 
    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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  • 145
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    International Journal of Quantum Chemistry 3 (1969), S. 763-766 
    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: It is shown that the uncoupled approximation of Dalgarno with the approximate form of the Hartree-Fock operator gives no bound for the second order energy.
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  • 146
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    International Journal of Quantum Chemistry 3 (1969), S. 753-762 
    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 distribution of electronic charge in cubic boron nitride is investigated using the bond orbital wave functions recently calculated by Coulson and Doggett. Plots of the one-electron density function, in the (110) plane, are found to be insensitive to the choice of atomic basis functions, in contradistinction to the previously calculated effective atomic charges. A number of structure amplitudes are also calculated for each of the bond orbital wave functions.
    Additional Material: 5 Ill.
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  • 147
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    International Journal of Quantum Chemistry 3 (1969), S. 795-822 
    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 correspondence rules between the algebra of coupling coefficients of the special unitary group SU(2) and the associated algebra of a subgroup G of SU(2) are presented. The matrix elements of the irreducible representations of G are written in a convenient quantization scheme and different relations between these matrix elements and the Clebsch-Gordan coefficients of G are derived. Such a formalism is appropriate for numerous spectroscopic problems. As an example, it is applied to crystal field theory and electron paramagnetic resonance. General formulas from which a large number of results are rederived and generalized in a straightforward fashion are given. Numerical values of coupling coefficients for the tetragonal and cubic groups are listed in the Appendix.
    Additional Material: 8 Tab.
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  • 148
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    International Journal of Quantum Chemistry 3 (1969), S. 913-930 
    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 theory for handling non-orthogonal radial orbitals of two shells of atomic electrons based on the mathematical apparatus of irreducible tensor operators is presented. The general expressions for one- and two-electron operator matrix elements are given.
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  • 149
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    International Journal of Quantum Chemistry 3 (1969), S. 249-267 
    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: Results obtained by various quantum-mechanical approaches in studying localized states on crystal surfaces are summarized and discussed. The one- and many-electron aspects of the problem are compared and shown to lead to similar results. Emphasis is laid upon localized chemisorption states on intrinsic semiconductors. The problem of the calculation of chemisorption heat on solid surfaces is also mentioned.
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  • 150
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    International Journal of Quantum Chemistry 3 (1969), S. 873-879 
    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 system C2H5+ has been investigated as ethyl cation and as protonated ethylene using the SCF-MO-LC(LCGO) method. Equilibrium distances and angles have been estimated by different potential curves. No difference in total energy was found between the π- and the σ-complex.
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  • 151
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    International Journal of Quantum Chemistry 3 (1969), S. 903-911 
    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 the leading term for very large R of the Casimir-Polder potential, that is the term varying as R-7, arises in second-order perturbation theory applied to the interaction Hamiltonian - \documentclass{article}\pagestyle{empty}\begin{document}$ - \sum\limits_\sigma {\frac{1}{2}\alpha (\sigma){\rm E}^{ \bot ^2 } (\sigma)} $\end{document}. The generalization to anisotropic molecules is calculated and the angular dependence of the long range intermolecular potential in this case is given explicitly in terms of the principal polarizabilities and their corresponding directions of the two molecules.
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  • 152
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    AIChE Journal 15 (1969), S. 155-156 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 153
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    AIChE Journal 15 (1969), S. 18-24 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effects of pore diffusion in the catalytic oxidation of ethylene on copper oxide-alumina have been studied by varying the catalyst size and maintaining constant the ratio of the tube to the pellet diameter. Hydrocarbon analysis was determined with a flame ionization detector; infrared analyzers were used to determine carbon monoxide and carbon dioxide concentrations. Other reaction products were analyzed with a gas chromatograph. Curvature of the Arrhenius plots and increase in reaction order with temperature indicated a transition region between kinetic control at lower temperatures and pore diffusion control at higher temperatures. A calculation procedure which was developed to predict the conversion considering pore diffusion effects provided satisfactorily agreement between calculated and experimental results.
    Additional Material: 10 Ill.
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  • 154
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    AIChE Journal 15 (1969), S. 35-39 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rate of attrition of a catalyst sample, of a single particle size, can be expressed by a simple function of initial diameter and time. The initial rate is a function of initial diameter, whereas the decrease in attrition rate of a catalyst of a given size as it ages depends only on time.The attrition equation for a single size of particles is introduced into the particle size distribution function and, through mathematical analyses, yields a relationship for the attrition of a full size-range catalyst. The form of this relationship, which includes terms for attritability and severity of attrition conditions, is verified by laboratory and commercial attrition data on two full-range catalysts. The size distribution of an attrited sample is not expressible in simple analytical form, but is readily obtained by numerical analysis.
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  • 155
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    AIChE Journal 15 (1969), S. 94-100 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Process design computations are represented by directed graphs whose edges correspond to streams of information flow between computational units. Algorithm I-R extends existing algorithms for finding the minimal sized blocks of units between which no recycle exists. Algorithm II-R orders the sequence of unit computations within a block to minimize the number of recycle parameters. Algorithm III-R uses the concept of indexing to order computations which evade algorithm II-R. This work is directed toward the evolution of efficient programs for computer-aided process design.
    Additional Material: 17 Ill.
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  • 156
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The permeation of carbon dioxide through polyethylene membranes has been studied at pressures up to 54.4 atm. and at temperatures above and below the critical temperature of the gas (31.0°C.). The permeability coefficient is independent of pressure at the highest experimental temperature (61.0°C.), but becomes increasingly pressure-dependent as the temperature is lowered. The principle of corresponding states can be used to correlate the solubility of both gases and vapors in polyethylene over a wide range of temperatures. This principle can also be invoked to obtain an upper limit for the penetrant pressure above which the permeability coefficient becomes pressure-dependent. The effect of pressure on the permeability, solubility, and diffusivity of gases and vapors in polyethylene is discussed in some detail.
    Additional Material: 5 Ill.
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  • 157
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    AIChE Journal 15 (1969), S. 3-3 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 158
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    AIChE Journal 15 (1969), S. 146-149 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 159
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    AIChE Journal 15 (1969), S. 214-219 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Differently shaped bubbles were observed growing during nucleate boiling of water at atomspheric pressure. The surface temperature beneath the bubbles was measured simultaneously with a fast response surface thermocouple. The evaporation from the base necessary to account for the observed cooling was calculated. A comparison of the ratio of vapor volume formed at the base to the total volume of the bubble shows a dependency on bubble shape. The ratio is smallest for spherical bubbles, largest for hemispherical and intermediate for oblate bubbles.
    Additional Material: 9 Ill.
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  • 160
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Solubilities and diffusivities of various gases (helium, nitrogen, carbon dioxide, argon, neon, krypton, and monochlorodifluoromethane) in molten or thermally softened polymers (polyethylene, polypropylene, polyisobutylene, polystyrene, and polymethylmethacrylate) have been correlated with structural characteristics, temperature, and pressure. Temperature dependence of both Henry's Law constants and diffusivities were of the Arrhenius equation form. No appreciable effect of pressure was found for either Henry's Law constants or diffusivities up to 300 atm. Earlier correlations for Henry's Law constants in solid polymer systems were found to be inapplicable for molten and thermally softened polymers. New correlations were developed individually for the latter systems. The correlating factor used was the gas Lennard-Jones force constant. Existing correlations for diffusivities were also found not to apply to molten and thermally softened systems. New correlations were again developed on an individual polymer basis. These related diffusivity to gas Lennard-Jones collision diameter or molecular diameter. Generalized correlations were also developed that held for a number of polymers. These were for both Henry's Law constants and diffusivities.
    Additional Material: 9 Ill.
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  • 161
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    AIChE Journal 15 (1969), S. 303-305 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 162
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    AIChE Journal 15 (1969) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 163
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    AIChE Journal 15 (1969), S. 276-281 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes a numerical procedure for optimizing a large set of interconnected systems with respect to a given index of performance. The method automatically constructs the vector differential equation of the complete system from (a) the vector differential equations describing the behavior of the components of the system and (b) the manner of their interconnection. A hill-climbing method is then used to select optimum values of the system's parameters to maximize a given index of performance. An example of the procedure applied to a high order system is included.
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  • 164
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    AIChE Journal 15 (1969), S. 442-449 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An absolute rate theory based on a plausible model of the activated state, was developed for the interfacial kinetics of crystal growth from the melt. Except for liquid metals the theory predicts the growth rates of pure materials within about an order of magnitude. A microinterferometric technique was employed to observe liquid compositions near the faces of crystals growing from binary melts. For the simple eutectic system composed of salol and thymol, the theory represents the composition and temperature dependence of the growth rate.
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  • 165
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    AIChE Journal 15 (1969), S. 308-311 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 166
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    AIChE Journal 15 (1969), S. 327-333 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The laminar boundary layers on a moving continuous flat surface in non-Newtonian fluids characterized by the power law model are investigated using exact and approximate methods. Both pseudoplastic and dilatant fluids are considered. Numerical solutions of the boundary-layer equations are obtained for values of the parameter n in the power law model ranging from 0.1 to 2.0. An integral solution of the momentum equation, which can be used to obtain values of the dimensionless shearing stress that are in good agreement with the exact values, is developed. An integral solution to the energy equation is also presented.
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  • 167
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    AIChE Journal 15 (1969), S. 357-362 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Forced convection heat transfer from vertical cylinders normal to an air-water spray flow stream was measured over an air velocity range from 60 to 140 ft./sec. and a water spray density range from 0.03 to 0.50 lb.m/(min.) (sq. in.). Local heat transfer coefficients were determined at 15 deg. intervals around the circumference of both a 1.5 and a 1.0 in. diam. cylinder. It was found that the addition of 0.426 lb.m/(min.) (sq. in.) of water spray to a 133 ft./sec. air stream raised the stagnation point heat transfer coefficient from 45 to 1,650 B.t.u./(hr.) (sq. ft.) (°F.). Similar intensification was found for other angles around the cylinder circumference; however, the magnitude decreased with increasing distance from the stagnation point. Local heat transfer coefficients were normalized with respect to their corresponding stognation point values and plotted parametrically as a function of angle and air velocity. These profiles showed that the normalized heat transfer coefficients decreased with increasing air velocity at angles other than the stagnation point. Average cylinder heat transfer coefficients were calculated from the air-water data and two correlations were obtained relating these coefficients to the air and the water spray Reynolds number.
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  • 168
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    AIChE Journal 15 (1969), S. 387-392 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A study was made of the radiolytic oxidation of cyclohexane in aqueous solution by using cobalt 60 gamma radiation. In the presence of dissolved oxygen gas the reaction proceeds irreversibly with the formation of a number of oxidation products. Those identified were cyclohexanol, cyclohexanone, and hydrogen peroxide. Trace quantities of carbon dioxide were also detected in the liquid phase. Using a constant dose rate of 15 × 104 rad./hr. in all runs, radiation yields were G(C6H11OH) = 0.49, and G(C6H10O) = 1.08. When molecular oxygen was excluded from the system, neither cyclohexanol nor cyclohexanone was formed on irradiation. A simplified kinetic model based on competition by the various solutes in the system for a single primary radical species produced by radiolysis of the solvent molecules is developed. Results generated using the mathematical model are compared with the experimental data. Excellent agreement between the observed and computed trends is noted at radiation doses up to 50 × 104 rad.
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  • 169
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    AIChE Journal 15 (1969), S. 414-418 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The optimal unsteady control of a jacketed tubular reactor with and without heat generation due to chemical reaction in response to a step disturbance in the feed stream concentration is computed. More rigorous control action was found to be necessary for the case with heat generation than without heat generation. Convergence of the method was also investigated with fixed and free final time.
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  • 170
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    AIChE Journal 15 (1969), S. 434-441 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An analysis is performed of the strongly coupled heat and mass transfer processes which result from sublimation of mass from the walls of a duct into a flowing gas, the latent heat being provided solely by convective transfer from the gas. The flow is assumed to be laminar and hydrodynamically developed. Results are given for the streamward variations of the bulk and wall temperatures and mass fractions, of the heat and mass transfer rates, and of the local heat transfer coefficient. Representative temperature and mass fraction profiles are also presented. Entrance lengths characterizing the near approach to fully developed conditions are tabulated. Comparisons are made of the present results (based on a parabolic velocity profile) with those based on a slug flow velocity profile. A subsidiary analysis using the Lévěque model is also performed and the results compared with those of the principal solution.
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  • 171
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    AIChE Journal 15 (1969), S. 712-715 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The liquid that moves along the duct walls in the annular regime observed in gas-liquid flows often consists of a series of flow surges (roll waves) moving over a thin liquid film (base film). At a given gas velocity there is a critical flow rate of the liquid below which roll waves are not present. Measurements of the height and wall stress are presented to support the notion that the conditions in the base film are close to those which exist at the critical liquid flow rate.
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  • 172
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    AIChE Journal 15 (1969), S. 727-733 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Data are reported for heat transfer from water to melting ice spheres and for mass transfer in the case of dissolving spheres of pivalic acid suspended in water agitated in a stirred vessel. The transport coefficients are found to depend on agitator power input but not on agitator design, in agreement with the Kolmogoroff theory. These experimental results are used with others in the literature to develop a correlation involving Nusselt and Prandtl or Schmidt numbers together with a dimensionless group involving agitation power. The correlation is essentially independent of solid-liquid density ratio in the range 0.8 to 1.25, and in this range the gravity group also appears to be unimportant.
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  • 173
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    AIChE Journal 15 (1969), S. 592-596 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Heat transfer and pressure drop data were taken on commercial plate heat exchange equipment. Nusselt and Euler correlations were determined for each of the six commercial heat exchangers investigated. These correlations were combined to establish a single heat transfer-pressure drop relationship for any plate type of heat exchanger channel.The results of this investigation were tested by using the correlations developed in Part I of this series to predict pressure drop data for the commercial unit based on their channel geometries. These predicted pressure drops were then used with the results of this part of the series to predict and compare heat transfer data.The correlations developed in this work allow one to determine the heat transfer characteristics in a ribbed rectangular channel from the pressure drop characteristics of the channel in question.
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  • 174
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    AIChE Journal 15 (1969), S. 615-617 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 175
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    AIChE Journal 15 (1969), S. 829-836 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A generalized approach to reverse osmosis process design is presented for solution-membrane-operating systems characterized by the dimensionless parameters γ, θ, and λ defined in terms of the pure water permeability constant A, solute transport parameter (DAM/Kδ), mass transfer coefficient k on the high pressure side of the membrane, and the properties of the solution. Analytical expressions are derived, in terms of dimensionless quantities, for the change of volume of solution, concentration of the bulk solution and that of the concentrated boundary solution on the high pressure side of the membrane, the change in the permeating velocity of solvent water through the membrane, solute separation, and the other related quantities, at any instance, as a function of concentration of the product solution on the atmospheric pressure side of the membrane, or time from the start of the operation for reverse osmosis systems specified by γ, θ, and λ. The equations are applicable to membranes for which (DAM/Kδ) is independent of solute concentration and feed flow rate, and for aqueous feed solutions whose molar density can be assumed constant and whose osmatic pressure is proportional to mole fraction. The equations are developed first for the case of batch-by-batch operation, and their applicability to the flow case is then indicated.
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  • 176
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    AIChE Journal 15 (1969), S. 861-865 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The final stages of condensation polymerization are characterized by a rapid rise in molecular weight, as the condensation product is formed and diffuses out of the polymer. The process occurring is one of desorption accompanied by a chemical reaction. The penetration theory equations for a generalized condensation polymerization reaction have been solved and some solutions are presented. The penetration theory solution, obtained by finite-difference computations, is compared with an analytical solution for the special case of no diffusional resistance.
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  • 177
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    AIChE Journal 15 (1969), S. 933-935 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstracts.
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  • 178
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    AIChE Journal 15 (1969), S. 815-822 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equations were developed for evaluating the laminar flow behavior of high-solids suspensions from the physical properties of the liquid and solid components. A technique was developed for calculating suspension flow rates as a function of pressure drop. The technique is applicable to the design of pipe lines. Flow measurements were made in pipe-line viscometers of a unique design that minimized entrance and exit effects. Experimental flow data were obtained for suspensions consisting of nickel, alumina, copper, or glass solids in sodium, xylene, or glycerine vehicles with solids concentrations of 28 to 55 vol. %. The basis for the correlation of the data was an analytical investigation of the flow behavior that considered the particle-particle interaction that takes place in a settled suspension. The correlation equations fit all systems investigated. They take into account the effects of liquid viscosity, liquid and solid densities, particle size, size distribution, particle surface area, volume fraction of solids in the suspension, and volume fraction of solids at maximum settled conditions.
    Additional Material: 4 Ill.
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  • 179
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    AIChE Journal 15 (1969), S. 853-860 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A realistic CSTR model was developed and verified experimentally. The reaction studied was the exothermic, base sodium hydroxide catalyzed decomposition of hydrogen peroxide. The model was used to evaluate the usefulness of the following stability analyses: steady state analysis, local linearization and Liapunov's direct method through Krasovskii's theorem. The effect of control valve hysteresis on the system was also investigated.
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  • 180
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    AIChE Journal 15 (1969), S. 866-872 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The local volume average of the equation of motion is taken for an incompressible fluid flowing through a porous structure under conditions such that inertial effects may be neglected. The result has two terms beyond a pressure gradient: g, the force per unit volume which a flowing fluid exerts on a porous structure, and the divergence of the local volume-averaged extra stress tensor (viscous portion of the stress tensor).Constitutive equations for g are examined with the aid of the principle of material indifference. When g is assumed to be a function of the velocity of the fluid relative to the solid as well as various scalars, the usual results for a nonoriented (isotropic) porous structure are obtained. When g is assumed to be a function of the local porosity gradient as well, we derive a new expression for g applicable to oriented (anisotropic) porous structures.For a Newtonian fluid with a constant viscosity, the divergence of the local volume-averaged extra stress tensor is proportional to the Laplacian of the averaged velocity vector. Boundary conditions for the averaged velocity vector are discussed. Three problems are solved for the flow of an incompressible Newtonian fluid in a nonoriented permeable medium. These solutions, as well as an order-of-magnitude analysis, suggest that we may often neglect both the Laplacian of average velocity and the boundary conditions for the tangential components of averaged velocity at an impermeable wall.Two specific constitutive equations for g are proposed for the flow of incompressible Noll simple fluids in nonoriented porous structures. Flow through a porous medium bounded by an impermeable cylindrical surface is solved for these two constitutive equations, and the results are compared with previously available experimental data.
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  • 181
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    AIChE Journal 15 (1969), S. 3-155 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 182
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    AIChE Journal 15 (1969), S. 4-10 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dye tracer technique was utilized to measure the residence time distribution of the drops in a spray column, operating with a dispersed or a dense packing of drops, for a wide range of flow rates, in a 15 cm.in diameter, 150 to 160 cm. long column proper.For dispersed packing of drops and for flow rates below the onset of coalescence, the flow of the drops was approximately plug flow, with a variance of the residence time distribution of 0.095. For flow rates above the onset of coalescence within the column, the variance increased sharply to 0.55 and decreased at higher flow rates.For dense packing of drops the variance of the residence time distribution was in the range of 0.1 to 0.5. This variance is attributed to the effect of bypassing water and kerosene near the wall of the column. A mathematical model based on this effect showed reasonable fit with the experimental results. This model predicts an approach to plug flow of the drops for large diameter columns.
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  • 183
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    AIChE Journal 15 (1969), S. 57-63 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A sensitivity matrix is defined as a measure of trajectory deviations to small parameter variations of both open and closed loop controlled nonlinear parabolic and first-order hyperbolic systems. In general the parameters may enter through the system equations or the boundary conditions and may be time or spatially dependent. The introduction of a positive measure of the sensitivity, the norm of the sensitivity matrix, into the performance index is shown to be effective in limiting the trajectory deviations due to the parameter variations. The open and closed loop control of a double pipe heat exchanger is analyzed with the open loop problem solved by an approximate procedure. The sensitivity reformulation is successful in reducing trajectory sensitivity, however at the cost of decreased overall performance.
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  • 184
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    AIChE Journal 15 (1969), S. 81-85 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Axial dispersion was studied experimentally for turbulent flow through a 1 1/4-in. piping system containing 90 deg. elbows. The Reynolds number range was 15,400 to 96,555. The imperfect pulse tracer technique was used with the axial dispersion numbers being obtained from the difference in variances of concentration-time curves observed at two points in the system.Elbows interconnected by short lengths of pipe with each succeeding one reversed so as to cause a change in the direction of flow, increased axial dispersion by 35 to 61% over that expected for straight pipe, while the same elbows turned so as to form a helix decreased the dispersion substantially; however, the amount of axial dispersion was still 8 to 22% greater than that observed for straight pipe.The equivalent lengths of the elbows depend upon both their arrangement and the Reynolds number. Closely placed, helically arranged elbows required equivalent lengths of from 2.9 to 5.1 diam., while a reversed arrangement required 6.9 to 11.6 diam. Elbows separated by a developing length and randomly arranged yielded an equivalent length range of 3.6 to 10.6 diam. The geometical l/d ratio of the elbows used was 2.05.
    Additional Material: 7 Ill.
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  • 185
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    AIChE Journal 15 (1969), S. 100-105 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A region into which particles arrive in a random manner, remain a random amount of time, and then leave is considered. This model is used in penetration theories of heat and mass transfer. From observations of the number of particles present at any time, it is desired to estimate arrival and exit statistics, residence time statistics, and average rates of transfer across the region. Assuming arrival is a Poisson process, equations governing the above statistics are derived. Some problems in spectral analysis arising from the use of nondifferentiable stochastic processes are solved. Estimators for important parameters are discussed, and it is shown that generally they are biased. A derivation linking the rate of transfer across the region with the rates of transfer of particles is obtained and compared with other such results.
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  • 186
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    AIChE Journal 15 (1969), S. 126-127 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 187
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Differential equations were derived to describe the system characterized by a rapid, irreversible reaction of a fluid species in a flowing fluid with a fixed bed of solids in which the reaction rate was controlled by mass transfer of the reacting fluid from the bulk fluid to the reaction site in the solid. Two kinds of mass transfer resistances were assumed, external or film diffusion resistance, and internal pore diffusion resistance. The set of differential equations were solved by a finite-difference method for both the generalized case and for the specific case of reaction of hydrogen in a stream of helium with fixed beds of copper oxide pellets.The hydrogen-copper oxide reaction is one step in a proposed method for removal of hydrogen as a contaminant in the helium coolant of nuclear reactors. This reaction was experimentally investigated in tests with both differential and deep beds of copper oxide in the temperature range of 400 to 600°C., at pressures of 10.2 to 30.0 atm., with gas mass flow rates of 0.0050 to 0.050 g./sq.cm.-sec, and with inlet hydrogen concentrations of 0.0008 to 1.21 vol. %. These tests showed that the system could be described by the two rate-limiting steps: film and pore diffusion of hydrogen. Differential-bed tests were used to establish hydrogen transport properties within the porous copper oxide pellets, and tests with deep beds were used to establish external mass transport properties.Generalized breakthrough curves were determined by a computer solution of the mathematical model. These curves can be the basis for design of fixed-bed copper oxide oxidizers for gas-cooled, nuclear reactor purification systems and for design of any fixed-bed system which follows the assumed reaction mechanism.
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  • 188
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    AIChE Journal 15 (1969), S. 133-135 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 189
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    AIChE Journal 15 (1969), S. 136-137 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 190
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    AIChE Journal 15 (1969), S. 144-146 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 191
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    AIChE Journal 15 (1969) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 192
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 193
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    AIChE Journal 15 (1969), S. 171-177 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liapunov's direct method is used to establish a finite region of asymptotic stability for nonlinear systems with an arbitrary number of state variables. The procedure is a geometric one in multidimensional space which uses the Fletcher-Powell minimization technique to find the maximum time derivative of the Liapunov function on the closed Liapunov hypersurface. Three detailed examples are presented, the first being the classical 2-variable CSTR with heat transfer and the third being a 32-variable 16-stage model of an adiabatic tubular reactor with axial diffusion.
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  • 194
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    AIChE Journal 15 (1969), S. 194-199 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A shell progressive kinetic model is used to determine the temperature rise in a spherical pellet for a gas-solid diffusion controlled reaction. The effects of heat and mass transfer resistances in the gas film as well as inside the pellet are investigated. The predicted temperature rise may be severe enough to cause sintering to catalyst pellets in which reactions such as combustion of coke occur.
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  • 195
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    AIChE Journal 15 (1969), S. 220-226 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 196
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    AIChE Journal 15 (1969), S. 208-214 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiments have been carried out to measure the permeation of tritium-labeled toluene through polyethylene films fully swollen with chlorobenzene, mesitylene, cumene, toluene, ethylbenzene, cyclohexane, tetrahydronaphthalene, and decahydronaphthalene. The results show characteristic Arrhenius temperature dependence over the range 25 to 40°C. The permeation of toluene through the films appears to be enhanced by increased solubility of the swelling agent (estimated from the work of others) in the film and there also appears to be a rough correlation between permeability of toluene and the boiling points and vapor pressures of the swelling agents. The range of permeabilities measured at 25°C. is 2.09 × 10-7 to 0.51 × 10-7 sq.cm./sec., the extremes of measured permeation activation energy, Ep, are 11.41 to 16.68 kcal./mole, and the pre-exponential factor, Po, falls within the interval 36.59 to 1.29 × 105 sq.cm./sec. A very definite linear relationship or compensation effect is evident between Po and Ep. Except as mentioned above, none of these quantities appears to correlate uniformly with the following properties of swelling solvent: molecular weight, dipole moment, specific gravity, vapor pressure, boiling point, heat of vaporization, critical temperature, viscosity, surface tension, molar volume, molecular area or other molecular dimensions.
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  • 197
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    AIChE Journal 15 (1969), S. 245-249 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Oxidation-reduction rates have been determined in stirred liquid-liquid systems wherein tetravalent cerium ions in a continuous aqueous phase were reduced by tetrachlorohydroquinone contained in dispersed organic droplets. Kinetic data obtained (using low volume fractions (〈0.06) of dispersed organic phase) indicate that the rate of reduction of ceric cerium is proportional to the extent of the interfacial area of the stirred liquid-liquid system. Two possible rate-limiting mechanisms are discussed to explain the observed kinetic behavior.This liquid-liquid electron exchange system might find potential use as a chemical tool for measuring changes in interfacial area as influenced by various mixing parameters.
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  • 198
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    AIChE Journal 15 (1969), S. 256-263 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure-temperature data were obtained along isenthalps for nitrogen, methane, and three ternary nitrogen-methane-ethane mixtures. These data were differentiated to obtain Joule-Thomson coefficients over the temperature range from ambient to 200°K. and at pressures from 165 atm. to about 5 atm. Data for nitrogen was obtained down to 140°K.The resulting Joule-Thomson coefficients were compared with predictions based on the Beattie-Bridgeman and Benedict-Webb-Rubin equations of state and on the virial equation of state truncated after the third virial coefficient. These comparisons show that the Benedict-Webb-Rubin equation could predict the data with a deviation averaging 1.7%. The Beattie-Bridgeman predictions were highly dependent upon the mixture rules used, with the best set of mixture rules giving an absolute average deviation of 4.8%. Predictions using the virial equation with virial constants obtained from the Lennard-Jones potential energy function using a geometric mean minimum potential energy deviated from the experimental data by 5%.In all of these comparisons, the virial coefficients of ethane appear to be in greatest uncertainty, and the predictions of mixture data high in ethane least satisfactory. Thus it appears that improved data on the pure components, particularly ethane, are vital to any satisfactory evaluation of mixture properties.
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  • 199
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    AIChE Journal 15 (1969), S. 281-288 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of ultrasonic vibrations on heat transfer to water and methanol by natural convection and by boiling were measured at three ultrasonic energy levels with frequency ranging from 20.6 to 306 kcycles/sec., using electrically heated platinum wires of diameters 0.007 and 0.010 in. Up to an eight-fold increase in heat transfer coefficient was obtained in natural convection, but the effects diminished with increased temperature difference and became negligible in the well-developed nucleate boiling region. High-speed photographs showed that the increase was due to the motion of cavitation bubbles on the wire surface. The heat transfer results were correlated by local cavitation activity values measured by a technique developed for this work.
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  • 200
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    AIChE Journal 15 (1969), S. 301-303 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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