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  • 1995-1999  (513)
  • 1995  (513)
  • Computational Chemistry and Molecular Modeling  (513)
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 1-2 
    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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  • 2
    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 Neglect of Diatomic Differential Overlap approximation is examined in terms of a polynomial expansion in Γ. The expansion is based upon the Legendre or Chebyshev approximation as developed in Part II. Analogous to the theorems of Chandler and Grader, NDDO cannot be justified for one-electron integrals and only partially for the two-electron repulsion integrals. © 1995 John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995) 
    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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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 607-615 
    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 intermolecular potentials for the X 2σ and A2Π states of Li… Ar were studied by a variety of multiconfiguration, single-configuration, and perturbation methods (CASPT2). The A 2Π excited state was calculated to have a well depth of 811 cm-1 at an internuclear separation of 2.59 Å, in excellent agreement with the 810 cm-1 derived from experimental data. A smaller well of 77 cm-1 was found for the X 2σ ground state at an intermolecular separation of 4.8 Å. These results are in better agreement with experimental results than were the previously reported pseudopotential calculations. The comparison of CI calculation with the CAPST2 results shows that the latter is able to give good results for interacting metal-rare gas systems. © 1995 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 627-633 
    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: Atomic charge and momentum densities of 91 atoms (He—U) are classified in terms of their L1, L2, and entropic measures of distance from the densities of the preceding atoms. The relationship between these distances and the first ionization energies is also considered. © 1995 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 119-124 
    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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  • 7
    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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  • 8
    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: Nonintegrable Poincaré systems with a continuous spectrum (so-called large Poincaré systems, LPS) lead to the appearance of diffusive terms in the frame of classical or quantum dynamics. These terms break time symmetry. They lead, therefore, to limitations to classical trajectory theory and of wave-function formalism (Schrödinger's equation). These diffusive terms correspond to well-defined classes of dynamical processes (i.e., so-called vacuum-vacuum transitions). The diffusive effects are amplified in situations corresponding to persistent interactions. As a result, we have to include, already, in the fundamental dynamical description the two basic aspects, probability and irreversibility, which are so conspicuous on the macroscopic level. We have to formulate both classical and quantum mechanics on the Liouville level of probability distributions (or density matrices). For integrable systems, we recover the usual formulation of classical or quantum mechanics. Instead of being primitive concepts, which cannot be further analyzed, trajectories and wave functions appear as special solutions of the Liouville-von Neumann equations. This extension of classical and quantum dynamics permits us to unify the two concepts of nature that we inherited from the nineteenth century, based, on the one hand, on dynamical time-reversible laws and, on the other, on an evolutionary view associated to entropy. It leads also to a unified formulation of quantum theory, avoiding the conventional dual structure based on Schrödinger's equation, on the one hand, and on the “collapse” of the wave function, on the other. A dynamical interpretation is given to processes such as decoherence or approach to equilibrium without any appeal to extra dynamic considerations (such as many-world theory, coarse graining, or averaging over the environment). There is a striking parallelism between classical and quantum theory. For large Poincaré systems (LPS), we have, in general, both a “collapse” of trajectories and of wave functions. In both cases, we need a generalized formulation of dynamics in terms of probability distributions or density matrices. Since the beginning of this century, we have known that classical mechanics had to be generalized to take into account the existence of universal constants. We now see that classical as well as quantum mechanics also have to be extended to include unstable dynamical systems such as LPS. As a result, we achieve a new formulation of “laws of physics” dealing no more with certitudes but with probabilities. This formulation is appropriate to describe an open, evolving universe. © 1995 John Wiley & Sons, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 131-147 
    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 Coulomb-Hole-Hartree-Fock method introduced by E. Clementi in the early 1960s and reparametrized more recently by S. Chakraworty and E. Clementi to compute the correlated electronic energy in atomic systems, is here extended to compute molecules. The new parametrization is obtained empirically by fitting first and second atomic ionization potentials from He to Ca and a few diatomic molecules. The present formulation makes use of either one or more determinants in order to ensure proper dissociation products, following the early proposal of G.C. Lie and E. Clementi in the context of density functional computations for molecular systems. The new formulation is tested against the dissociation energies of a large number of molecules and it is found satisfactory. © 1995 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 149-160 
    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 new form of second-order multireference perturbation theory coupled with finite-field perturbation theory is applied to evaluate some one-electron molecular properties. Several possible definitions of the zeroth-order Hamiltonian are considered and results tested against bench-mark full CI calculations. © 1995 John Wiley & Sons, Inc.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 161-181 
    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 relativistic Kepler problem is discussed, with emphasis on the exact supersymmetry of the problem. It is shown that the supersymmetry is generated by the Johnson-Lippmann operator. Two related operators are found to generate new supersymmetries in an extended function space. Each of these supersymmetries may be disguised as radial supersymmetries. The radial supersymmetries are discussed and it is shown that each of them defines a normal-mode representation of the hydrogen-atom radial functions. Thus, one obtains two different, but equivalent, analytical expressions for these functions. The expressions are well known, but are rederived here in the light of the new understanding. Finally, the nonrelativistic image of the relativistic supersymmetry is constructed and its generators shown to be identical with those recently presented in the literature. © 1995 John Wiley & Sons, Inc.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 183-187 
    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 the present article, we have attempted a systematic procedure for use of biorthogonal techniques to the configuration interaction studies in molecules using nonorthogonal valence bond (VB) orbitals. The procedure developed is integral-driven and a program based on this has been developed. Test runs of the program have been carried out in case of full and truncated configuration spaces. © 1995 John Wiley & Sons, Inc.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 189-205 
    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 introduces a set of localized orthonormal functions to serve as basis functions for quantum calculations. They are defined to be eigenfunctions of the position operator in a function space. Their properties, including their variances, for a one-dimensional system are developed. The application to simple harmonic motion is considered as an example and, in particular, the time evolution of an initially localized function is calculated and shown to be periodic. The theory can be interpreted as producing a discrete quantization of space with Hamiltonian interactions that are predominantly between nearest neighbors. These functions can also be used in approximate calculations. To illustrate their accuracy, the example of a Morse oscillator treated as a perturbation of a harmonic oscillator is reconsidered. It is shown that the localized functions in a variational calculation lead to a result that is a good approximation for the lowest states. Furthermore, the use of a wave function that is defined only at discrete points can be justified as the first approximation to this, so that its accuracy can also be discussed. © 1995 John Wiley & Sons, Inc.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 207-228 
    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 performance of the quasi-degenerate many-body perturbation theory up to the third order is investigated for the ground state, five excited states, and the first quintet of a simple four-electron H4 model system consisting of two stretched hydrogen molecules, in which the degree of quasi-degeneracy can be continuously varied from a nondegenerate to a full degenerate situation. We employ a DZP basis set. The effect of intruder states is considered and a comparison with other multireference correlation techniques is also provided. Finally, a criterion for the model space to be quasi-degenerate will be reformulated and generalized. © 1995 John Wiley & Sons, Inc.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 245-253 
    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 generalized interpretations of the high-energy band (HEB) within the photoelectron spectras (PES) of alkanes, usually referred to as the C2s band, have been suggested. The quantum chemical one consists of attributing to the HEB of any alkane (CnH2n+2) the chain of n similiar orbitals ηk (k = 1…n), each of them containing mainly one 2sc AO and some contributions of another four orbitals from its nearest environment. The structure of each orbital ηk has been shown to be similar to that of the lowest totally symmetric MO of methane. The chemical interpretation of the same band involves relating it and the definite subspectrum of the full chemical graph of alkane, associated mainly with its C skeleton. The interrelation of these two complementary interpretations follows from the one-to-one correspondence between the orbitals ηk and the CH2(CH3) groups in alkane. © 1995 John Wiley & Sons, Inc.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995) 
    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
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 55 (1995), S. 1-2 
    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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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 55 (1995), S. 23-34 
    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 intersystem crossing (ISC) between the lowest triplet and singlet states occurring in the reaction of atomic oxygen with ethylene was studied. The importance of spin-orbit coupling (SOC) in oxirane biradicals (ĊR′R″ - CRR* - Ȯ) is stressed through calculations where the spin-orbit matrix elements over the full Breit-Pauli SOC operator has been obtained in the singlet-triplet crossing region. The calculations are performed with a multiconfigurational linear response approach, in which the spin-orbit couplings are obtained from triplet response functions using differently correlated singlet-reference-state wave functions. Computational results confirm earlier semiempirical predictions of the spin-orbit coupling as an important mechanism behind the ring opening of oxiranes and addition of oxygen O(3P) atoms to alkenes. © 1995 John Wiley & Sons, Inc.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 423-432 
    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 dynamics of Jahn-Teller systems has recently been discussed in terms of generalized electronic charge and current densities in nuclear-coordinate space. The introduction of the electronic phase as a function of both electronic and nuclear coordinates, in addition to the electronic density, was a crucial component of this formulation. Here, a densitybased treatment of Born couplings is derived from first-principles quantum mechanics beyond the Born-Oppenheimer approximation. Because of the degenerate electronic configuration of a Jahn-Teller molecule, there are an infinite number of ways in which the charge distribution can be oriented for the same energy, leading to a vanishing bond hardness for the molecule in the symmetric nuclear configuration. Further, the moving nuclear framework serves as the perturbation necessary to define the orientation of the charge density, leading to unhindered rotation of the charge cloud. This leads to the dynamical Jahn-Teller problem, namely, the coupling of electronic and nuclear motions through the Born coupling terms. Applications to superconductivity theory are discussed. © 1995 John Wiley & Sons, Inc.
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 453-476 
    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: Recent reactivity concepts formulated within charge analysis (CSA) are outlined. The charge stability criteria of equilibrium states in open and closed systems are conveniently characterized in terms of the condensed reactant hardness quantities of reactants; their implications for catatytic systems are examined. A use of characteristics associated with selected collective charge displacement modes, including the populational normal modes and minimum-energy coordinates, as diagnostic tools in the theory of chemical reactivity is proposed. The importance of the mapping relations between modes defined in the electron population and nuclear position spaces, respectively, as the unifying concept linking the conjugate charge and geometry displacements, is commented upon. Recent results for model catalytic clusters are used to illustrate some of the concepts introduced. Finally, the relevant contributions to the quadratic interaction energy between reactants are reexamined and expressed in terms of relevant charge sensitivities. © 1995 John Wiley & Sons, Inc.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 499-508 
    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 local density approximation (LDA) to exchange and correlation effects has well-known limitations. The nonlocal weighted density approximation (WDA) corrects some of those defects. This is illustrated here by applications to free atoms and small atomic clusters. The WDA also induces a nonlocal kinetic energy functional that is tested for atoms. © 1995 John Wiley & Sons, Inc.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 53 (1995), S. 265-273 
    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 order to avoid the violation of basic principles of macroscopic reversibility and detailed balance, we propose a cell kinetic model for atom-photon interactions instead of Enstein's classical photon kinetic mechanism. Our model can be interpreted as a generalization of either mass action law or Einstein's original scheme. © 1995 John Wiley & Sons, Inc.
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  • 23
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 83-93 
    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 potential energy surface for the first step of the alkaline hydrolysis of methyl acetate was explored by a variety of methods. The conformational search routine within SPARTAN was used to determine the lowest energy AM1 and PM3 structures for the anionic tetrahedral intermediate. Ab initio single point and geometry optimization calculations were performed to determine the lowest energy conformer, and the linear synchronous transition (LST) method was used to provide an initial structure for transition state optimization. Transition states were obtained at the AM1, PM3, 3-21G, and 3-21 + G levels of theory. These transition states were compared with the anionic tetrahedral intermediates to examine the assumption that the intermediate is a good model for the transition state. In addition, the Cramer/Truhlar SM3 solvation model was used at the semiempirical level to compare gas phase and aqueous alkaline hydrolysis of methyl acetate. © 1995 John Wiley & Sons, Inc.
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 123-136 
    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 report quantum chemical semi-empirical calculations of the geometries and the electronic structures (at AM1 and INDO/s levels) of three nonsteroidal antiinflammatory drugs (NSAIDs), namely, benoxaprofen, chlorpromazine and piroxicam, and a piroxicam metabolite, that have undesirable phototoxic effects. Our calculated electronic spectra in gas phase and in water fit reasonably well the observed spectral data. The wavelength of the absorption maxima are not significantly affected by changing from gas phase to water (at the SCRF level). We were able to assign the observed bands to the calculated transitions. We found also that the spectrum of the piroxicam metabolite actually responsible for the phototoxicity cannot be understood on the sole basis of one of the tautomers. We hope that these finding will be useful for the understanding of the photochemical events that lead ultimately to the biological effects. © 1995 John Wiley & Sons, Inc.
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  • 25
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 145-153 
    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: Ab Initio crystal orbital calculations on three-dimensional crystals/crystallohydrates of a number of diprotonated mononucleotides have been performed using the CRYSTAL92 routine package. The present results help to gain a deeper insight into the physical mechanisms of nucleic acid semiconductivity, as well as into the essence of intermolecular interactions and solvent effects in solid-state samples of nucleic acids. © 1995 John Wiley & Sons, Inc.
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  • 26
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 155-159 
    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 examine here spectroscopic properties of oxidized rubredoxin (Rdx) within the intermediate neglect of differential overlap method parameterized for spectroscopy. The Rdx structures are modeled using different length -SR residues bound to the Fe atom and the resulting effect on the absorption spectrum is examined. The corresponding ionization potentials are also calculated, and their dependence on the molecular charge is studied. This study suggests that models used to reproduce the redox properties of these important electron-transfer compounds must be carefully chosen. © 1995 John Wiley & Sons, Inc.
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  • 27
    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: Experimentally measured rates for the oxidation of p-substituted benzyl amines by bovine monoamine oxidase type B (MAO-B) derived from the literature were examined with respect to the effects of molecular (semiempirically (AM1) derived) electronic, steric, and lipophilicity parameters. These properties included vertical and adiabatic ionization potential, LUMO energy, the LUMO-HOMO difference, molecular hardness, absolute electronegativity, calculated log P values, molecular volume, surface area, and ovality. Substrate oxidation rates (log kcat/Km) were found to correlate with molecular ovality and vertical ionization potential while the rate of enzymatic (flavin) reduction associated with substrate oxidation (log kred) was described by a two-parameter model containing an ovality and an absolute electronegativity term. These results are consistent with an initial one-electron substrate oxidation mechanism. In previous work, use of classical Hansch analysis suggested that electronic terms were not important in the enzymatic reactions. This discrepancy may be related to nontransferability inherent in fragment approaches which assume that the substituent of interest behaves similarly in all molecular scaffolds. Analysis of substrate binding (log Kd) to the enzyme was described by a two-parameter model containing a calculated log P term as well as LUMO energy. The significant correlation found with LUMO energy is consistent with studies suggesting that this property is important for drug-receptor interactions. © 1995 John Wiley & Sons, Inc.
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  • 28
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 201-206 
    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: The integrated molecular transform (FTm) is a unitary structure index that has been successfully used for the correlation of 2- and 3-dimensional structure representations with their physicochemical and pharmacological properties. In the present instance the reported pKa values in a series of 30 compounds consisting of five subseries were correlated with their FTm indices. The omission of four outliers gave a moderate correlation across the entire series; within the individual subseries the correlations were considerably improved even with inclusion of the outliers. In general, the logarithmic transform of the pKa did not improve the correlations. This method gives a relatively simple means of estimating pKa in several structure classes. © 1995 John Wiley & Sons, Inc.
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  • 29
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    International Journal of Quantum Chemistry 56 (1995), S. 3-27 
    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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  • 30
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 61-78 
    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 current capabilities of density functional theory reach their limits somewhere in the region of weak inter- and intramolecular interactions. Hydrogen bonds can be treated, but not perfectly. The few results that have been obtained for dispersion-dominated van der Waals interactions are erratic. The generalized gradient approximation fails for charge-transfer complexes; hybrid functionals that incorporate a component of the Hartree-Fock exchange are promising, but the results depend strongly on the variant used. We recently used the adiabatic connection and coordinate scaling to develop correlation functionals based on a spin-polarized pair correlation function of the Colle-Salvetti type. A résumé of the current status of the functionals is given, including inter alia available validation results for various molecules and reactions, the water dimer, and charge-transfer complexes. It is shown that nonlocal schemes involving the kinetic energy density and, hence, the Laplacian of the electron density lead to an overall improvement of the calculated binding energies and equilibrium geometries, especially in cases when the current GGA schemes meet difficulties. © 1995 John Wiley & Sons, Inc.
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  • 31
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    International Journal of Quantum Chemistry 56 (1995), S. 109-115 
    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 Shannon information entropies of H2, C2, HF, OH, CH, CN, HOOH, C2H6, MeOH, CH3OCH3, CH3F, CH2O, CH3NH2, and C2H4F2 in both position and momentum space were calculated from HF/6-31G* wavefunctions. The results show that there were definite patterns between the information entropies, molecular geometric changes, and energies. The L1, L2, and 1d, measures were compared as effective measures of distance and with energetic changes. The use of these concepts in describing chemical structure is discussed. © 1995 John Wiley & Sons, Inc.
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  • 32
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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 all-electron, full-potential LCGTO-FF method, which has been used extensively to calculate the properties of ultrathin films and molecules, is extended to systems with 3-D periodicity in a new computer program called GTOFF. In this investigation, GTOFF is used to calculate the equilibrium properties of hcp beryllium. The structural parameters, binding energy, bulk modulus, and Poisson's ratio obtained with GTOFF are in good agreement with an earlier all-electron, full-potential calculation using the FLAPW method, confirming the high-precision of the present calculations. © 1995 John Wiley & Sons, Inc.
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  • 33
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    International Journal of Quantum Chemistry 56 (1995), S. 207-215 
    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 reaction of the PtSn system with the hydrogen molecule is studied theoretically. The results are compared with experimental reports of commercial-type catalysts and previous theoretical studies of Pt + H2 and Pt2 + H2 reactions. All the calculations were made by the ab initio MC-SCF + MRCI method including relativistic core potentials approximation. We consider two main geometrical approaches of the hydrogen molecule to the SnPt system: parallel and perpendicular. The theoretical and geometrical parameters were taken from our previous studies and from experiments. Many states were studied: Some of them are repulsive and others present weak capture of hydrogen; none scisse the H2 molecule. The main conclusion of this work is that the platinum activity, when Pt and Sn form alloys, is inhibited by the tin, suggesting that the interaction between the two metals occurs through an oxygen atom of the support. © 1995 John Wiley & Sons, Inc.
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  • 34
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    International Journal of Quantum Chemistry 56 (1995), S. 245-252 
    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 factorization of amplitudes of multiple excitations from those of elementary (single and double) excitations is only reliable when excitation energies are nearly additive. Such deviations from additivity may be important, especially in solid-state physics problems. Instead of introducing many-body operators in the coupled-cluster expansion, one may take into account the effect of these deviations from the additivity of excitation energies by proper energy-dependent corrections to the usual product of amplitudes. Their efficiency is illustrated on several model problems where the traditional approach gives poor results. © 1995 John Wiley & Sons, Inc.
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  • 35
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    International Journal of Quantum Chemistry 54 (1995), S. 271-271 
    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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  • 36
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    International Journal of Quantum Chemistry 54 (1995) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 37
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    International Journal of Quantum Chemistry 54 (1995), S. 273-279 
    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 apply the CFHH-GLF method, a modified version of our HH-GLF method, to directly solve the three-body Schrödinger equation for a set of He-like systems, including H-, He, Li+, Be2+, and B3+. Correlation functions with no adjustable parameters are determined from the cusp condition of the wave function. Our calculational results exhibit very fast and good convergence with hyperspherical harmonics (HH) and a generalized Laguerre function (GLF) and substantial improvement over the HH-GLF method. With only 36 HH and 6 GLF, we obtained the ground-state energy of -2.90371, -7.27988, -13.6555, and -22.0308 au for He, Li+, Be2+, and B3+, respectively. This compares with -2.89361, -7.26131, -13.6253, and -21.9859 au, respectively, by the HH-GLF method and Pekeris' results of -2.90372, -7.27991, -13.6556, and -22.0310 au, respectively. So, the inclusion of 36 HH and 6 GLF has yielded the precision of a few parts in 106 for He, Li+, Be2+, and B3+. However, our calculational results for H- are not so good. We analyzed the cause of this kind of exception and improved our calculations in this respect by using a slightly different correlation function. We finally obtained the ground-state energy of -0.527754 au for H- with 36 HH and 15 GLF, which is very near Pekeris' result of -0.527751 au and of the same order of precision as those achieved for other He-like ions. © 1995 John Wiley & Sons, Inc.
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  • 38
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    International Journal of Quantum Chemistry 54 (1995), S. 327-328 
    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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  • 39
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    International Journal of Quantum Chemistry 54 (1995) 
    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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  • 40
    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 effects of quartic anharmonicity on the quantum dynamics of a linear oscillator with time-dependent force constant (K) or harmonic frequency (ω) are studied both perturbatively and numerically by the time-dependent Fourier grid Hamiltonian method. In the absence of anharmonicity, the ground-state population decreases and the population of an accessible excited state (k = 2, 4, 6…) increases with time. However, when anharmonicity is introduced, both the ground- and excited-state populations show typical oscillations. For weak coupling, the population of an accessible excited state at a certain instant of time (short) turns out to be a parabolic function of the anharmonic coupling constant (λ), when all other parameters of the system are kept fixed. This parabolic nature of the excited-state population vs. the λ profile is independent of the specific form of the time dependence of the force constant, Kt. However, it depends upon the rate at which Kt relaxes. For small anharmonic coupling strength and short time scales, the numerical results corroborate expectations based on the first-order time-dependent perturbative analysis, using a suitably repartitioned Hamiltonian that makes H0 time-independent. Some of the possible experimental implications of our observations are analyzed, especially in relation to intensity oscillations observed in some charge-transfer spectra in systems in which the dephasing rates are comparable with the time scale of the electron transfer. © 1995 John Wiley & Sons, Inc.
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  • 41
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    International Journal of Quantum Chemistry 55 (1995), S. 47-52 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By expanding the atomic wave function in potential harmonics (PH) and generalized Laguerre functions (GLF), we derived the recurrence relation of the expansion coefficients and then performed calculations for four He-like three-body systems. In comparison with the complete set calculation (HHGLF), we find that the errors in eigenenergies introduced by the PHGLF scheme are approximately 0.00033, 0.00025, 0.00022, and 0.00021 au for the ground-state H-, He, Li+, and Be2+ systems, respectively, and that for excited states the error is slightly higher and decreases with the grand angular momentum. The present results indicate that the PHGLF scheme is such an efficient means to reduce the degeneracy of the hyperspherical harmonics (HH) for three-body problems that it can give more satisfactory results than can the HHGLF method with much smaller eigenmatrices. © 1995 John Wiley & Sons, Inc.
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  • 42
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    International Journal of Quantum Chemistry 55 (1995), S. 61-69 
    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 conformation structure of the tetrapeptide Ac-Lys-Ala-Leu-Ala-OMe, the repeat unit of a 30 residue peptide YAA(KALA)6LAA, and also its analog containing an unusual amino acid, (Aib): Ac-Lys-Aib-Leu-Aib-OMe, has been investigated by the PCILO method. The global/low-energy minima for all the residues lies at φ = -30° and ψ = 120°. In this conformation, the potential hydrogen-bonding sites are free, i.e., capable of intermolecular hydrogen bonding. As the angles lie closer to the collagen helical region and potential hydrogen-bonding sites are free, this structure is named the collagen-type helix. In aqueous solution, this structure is stabilized by solvation of the peptide bond. The local-energy minimum in all maps correspond to the right-handed helical region. The helix thus formed generates a pore of 3 Å along the helix axis, with one lateral hydrophobic side and the other hydrophilic side. The pore thus formed is cation-selective and accounts for the leakage of contents from vesicles. On the basis of the length of the helix and placement of the side chains of lysine and leucine, a model has been proposed for the aggregation and fusion of the vesicles. The amphipathic basic residues interact with the head groups of the acidic liposomes by extending toward the polar face of the helix to insert their charged moieties by overcoming the electrostatic repulsive forces between the opposing vesicles. © 1995 John Wiley & Sons, Inc.
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  • 43
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    International Journal of Quantum Chemistry 56 (1995), S. 677-687 
    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: Here, we have applied density functional methods, in combination with free energy hydration calculations, to calculate two-electron electrode potentials for quinones and naphthoquinones. While we find that the free-energy perturbation method, implemented within a molecular dynamics framework, is superior to the PM3 - SM3 continuum method for determining free energies of hydration, the computationally less expensive PM3 - SM3 method does perform well when there is not an internal hydrogen bond. Generally, all the density functional approaches investigated gave good energetics when applied to this problem, but the Beck '88 - Vosko - Wilk - Nusair combination of functionals for the exchange-correlation energy gave the best results. The density functional results are marginally better than the Møller-Plesset second-order perturbation results. Moreover, because the results are obtained using a thermodynamic cycle which involves taking differences in total energies, the results are not too dependent on the quadrature scheme used to calculate the exchange-correlation energy. By using semiempirically optimized geometries and the PM3 - SM3 method for determining free energies of hydration, it has been possible to calculate electrode potentials for a series of large molecules (naphthoquinones) to within about 30 mV of experiment. This result is extremely encouraging and shows that density functional methods offer great promise in the design of redox-active molecules such as bioreductive anticancer agents. © 1995 John Wiley & Sons, Inc.
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  • 44
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    International Journal of Quantum Chemistry 56 (1995), S. 707-732 
    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 time-dependent (TD), nonperturbative quantum fluid density functional equation of motion, developed in our laboratory, is numerically solved for studying the photoionization dynamics of the He atom under an intense, ultrasharp, ultrashort laser pulse. The generalized nonlinear Schrödinger equation is obtained through a hydrodynamical continuity equation and an Euler-type equation of motion. It yields the electron density, effective potential surface, and other density-based quantities from start to finish. Starting from the ground-state Hartree-Fock density for He at t = 0, various singlet and triplet states of singly and doubly excited (autoionizing) He as well as several states of He+ have been identified in the time-evolved electron density, by a Fourier transformation of the time variable of the complex autocorrelation function. Computer visualizations of the TD difference density and difference potential show distinctly nonlinear and extremely interesting geometrical features of the oscillating atom. Detailed mechanistic routes for multiphoton, sequential, and above-threshold ionization have been obtained, each route involving many states. The present, comprehensive method reveals the important physical features of the atom-laser interaction and the calculated results are consistent with current experimental and theoretical results. This emphasizes the validity of the hydrodynamical approach for studying TD quantum mechanical phenomena. © 1995 John Wiley & Sons, Inc.
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  • 45
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    International Journal of Quantum Chemistry 56 (1995), S. 763-769 
    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 article, some applications of lower bounds to density-dependent functionals in terms of radial expectation values are performed. These diverse applications include accurate upper bounds to the exact kinetic energy and to conjecture a wide set of relationships among radial and momentum expectation values. Some open questions for the improvement of these results are remarked upon. © 1995 John Wiley & Sons, Inc.
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  • 46
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    International Journal of Quantum Chemistry 56 (1995), S. 787-790 
    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: We present the first full ab initio calculation of second-order Raman spectra in semiconductors based on density functional perturbation theory. The method is applied to the Γ1+ spectra of the elemental semiconductors diamond, silicon, and germanium and reproduces the experimental data excellently. Using first-principles phonons, we also calculated the corresponding overtone densities of states and Γ1+ Raman spectra employing phenomenological polarizability coefficients. Finally, we analyze the results of the different approaches pointing out the relevance of a full first-principles derivation. © 1995 John Wiley & Sons, Inc.
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  • 47
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    International Journal of Quantum Chemistry 55 (1995), S. 187-203 
    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 coupled clusters singles and doubles (CCSD) method for calculations of open-shell systems with the single restricted Hartree-Fock (ROHF) reference determinant is extended by the noniterative triples to give CCSD(T). Our approach profits from the fact that (a) single- and double-excitation amplitudes are spin-adapted, which directly leads to a computationally less demanding algorithm than are nonadapted procedures and produces the spin-adapted CCSD wave function and (b) triple excitations calculated from converged spin-adapted (SA) CCSD amplitudes are also obtained more effectively. Altogether, computer demands of our SA CCSD(T) approach, applicable to high-spin open-shell cases which are well represented by a single-determinant reference is comparable to that for closed-shell systems. Our approach is not based on semicanonical orbitals, applied by Bartlett's group. However, we compare some other possible choices of ROHF orbitals to this “standard.” Numerical results for a series of atoms and molecules demonstrate little sensitivity to this selection. © 1995 John Wiley & Sons, Inc.
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  • 48
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    International Journal of Quantum Chemistry 55 (1995), S. 227-235 
    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: Ab initio all-electron fully relativistic Dirac-Fock self-consistent field and Dirac-Fock-Breit calculations are reported for the XeF4 molecule at various internuclear distances assuming the experimental D4h geometry with our recently developed relativistic universal Gaussian basis set. The nonrelativistic limit Hartree-Fock calculations were also performed for XeF4 at various internuclear distances. The calculated relativistic correction to the total energy of molecule at the Dirac-Fock level is ∼ -5856 eV, whereas the magnetic part of the Breit correction to the electron-electron interaction is calculated as ∼ 177 eV. The electron correlation effects were included in the nonrelativistic Hartree-Fock calculations using the second-order Møller-Plesset (MP2) theory, and the calculated correlation energy for XeF4 is -71 eV. The basis-set superposition error (BSSE) was estimated by using the counterpoise method for Xe and F. The inclusion of both the relativistic and electron correlation effects in the calculated total energies of F, Xe, and XeF4 predicts the Xe - F bond length and dissociation energy of XeF4 as 1.952 Å and 5.59 eV, respectively, which are in excellent agreement with the experimental values of 1.953 Å and 5.69 eV, respectively, for XeF4. The contribution of the electron correlation and relativistic effects to the dissociation energy of XeF4 is 8.11 and 0.05 eV, respectively. The Breit interaction, however, contributes only 0.02 eV to the dissociation energy of XeF4. Electron correlation is most significant for the prediction of an accurate value of dissociation energy, whereas relativistic effects are very important for the prediction of spin-orbital splitting as well as the energies of the orbitals, especially the inner orbitals of XeF4. © 1995 John Wiley & Sons, Inc.
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  • 49
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    International Journal of Quantum Chemistry 56 (1995), S. 1-1 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 50
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    International Journal of Quantum Chemistry 56 (1995), S. 113-122 
    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 geometries of the two most important tautomeric forms of adenine and the corresponding methyladenines are investigated by means of quantum chemical calculations at different level of sophistication, ranging from semiempirical methods to correlation corrected ab initio methods at second-order Møller-Plesset perturbation theory level (MP2). The relative stability of the N(7)H ↔ N(9)H tautomeric forms of adenine are investigated with highly correlation corrected methods, MP3 and MP4. The relative stability is also corrected for solvent interactions and compared with experimental information. N(9)H-adenine is predicted to be the most stable tautomer in both vacuum and in solution. The relative stability is predicted to be between 24.5 and 35.0 kJ/mol in vacuum depending on computation method. In water solution N(7)H-adenine is stabilized more by the solvent, and the corresponding relative energies were found to be between 4.9 and 10.2 kJ/mol. We also found that correlation effects are essential to describe the ground state geometry with a high accuracy. The geometries predicted by semiempirical methods and ab initio calculations without correlation correction show large deviations in some parts of the molecule compared to the MP2 results as well as compared with experimental geometries. © 1995 John Wiley & Sons, Inc.
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  • 51
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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: Theoretical and experimental studies were performed on a series of 1,4- and 1,6-dihydronicotinic acid derivatives to investigate their relative stabilities and factors contributing thereto. Ferricyanide-mediated oxidation studies indicated that not only did the 1,4-dihydropyridine derivatives oxidize more slowly than the 1,6-isomers, a finding consistent with previously published literature, but also that the ratio of the rates of reaction was constant. Thus, the 1,4-dihydropyridines oxidized 23-fold more slowly than did the 1,6-derivatives. Theoretical studies also indicated that the 1,4-dihydropyridines were more stable than the 1,6-isomers, as illustrated by lower calculated heats of formation, and were also more resistant to oxidation, as demonstrated by larger HOMO-LUMO energy gaps. An examination of the HOMO for the dihydropyridines showed that the 1,4-isomers were associated with a greater degree of homoaromatic and hyperconjugative stabilization as compared to the 1,6-dihydropyridines and that these factors did not appear to be significantly affected by substitution. These data suggest that the stabilizing properties associated with the 1,4-dihydropyridine system (i.e., greater contributions from the sp3 ring carbon and attached hydrogens) are systematically expressed providing an explanation for the constant difference in experimental reaction rates. © 1995 John Wiley & Sons, Inc.
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  • 52
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    International Journal of Quantum Chemistry 55 (1995), S. 377-392 
    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 g-tensors for the molecules NO2, CO2-, C3H5, H2CO+, and NF3+ are calculated at the unrestricted Hartree-Fock (UHF) level using the Rayleigh-Schrödinger perturbation approach. All one-electron terms have been evaluated, including the relativistic mass correction, the one-electron spin-Zeeman gauge correction, and a second-order term involving the spin-orbit coupling and the orbital-Zeeman interaction. The relative importance of the first-order terms is found to be quite substantial. For first-row molecules, their total contribution is often of the same order of magnitude as of the second-order contribution, in some instances even larger. A study on the basis-set dependence of these g-tensors has been conducted. At this level, the most important basis-set criterion is shown to be a satisfactory description of the valence regions. Finally, the gauge dependence of these g-tensor calculations has been systematically studied. This dependence seems to be substantially reduced for basis sets which include polarization functions. © 1995 John Wiley & Sons, Inc.
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  • 53
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    International Journal of Quantum Chemistry 55 (1995), S. 419-427 
    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 discrete variable representation method (DVR) is applied to the calculation of the J = 0 vibrational energy levels of the ground electronic state of nitrogen dioxide, a molecule which shows a large amplitude bending vibration. The Hamiltonian is expressed in Johnson hyperspherical coordinates and developed on a DVR basis set for each coordinate. A successive diagonalization-truncation method is applied which gives accurate values for the energy levels up to ≃ 7000 cm-1. © 1995 John Wiley & Sons, Inc.
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  • 54
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    International Journal of Quantum Chemistry 55 (1995), S. 441-457 
    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 energy curves for the ground and low-lying excited states of the AH2+ (A = Mg - Ar) dications have been calculated using high-level ab initio methods with large atomic orbital basis sets. Quasi-bound potential energy curves with local minima and deprotonation barriers have been found for most of the dications studied. The energies, tunneling lifetimes, and widths of the quasi-bound states have been calculated by numerical solution of the radial Schrodinger equation using the Numeov method. All these dications except ArH2+ have low-lying states which support quasi-bound vibrational states. The ArH2+ dication has a 2∏i potential energy curve with a minimum so shallow that it does not support any quasi-bound vibrational states. Results of our calculations are compared with previous ab initio calculations and available experimental data. © 1995 John Wiley & Sons, Inc.
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  • 55
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    International Journal of Quantum Chemistry 55 (1995), S. 493-493 
    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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  • 56
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    International Journal of Quantum Chemistry 56 (1995) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    International Journal of Quantum Chemistry 56 (1995), S. 9-17 
    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: An analysis of the analytical properties of the first iterate of the iteration-variation approach applied to small Gaussian expansions is reported in the case of the hydrogen atom. The first iterates embody important qualitative improvements such as a cusp near the origin and better asymptotic decay at large values of r. Actual values of the properties depend on the quality of the initial functions in such a way that for very small Gaussian expansions the variation step is necessary. © 1995 John Wiley & Sons, Inc.
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  • 58
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    International Journal of Quantum Chemistry 56 (1995), S. 27-42 
    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: Careful study of radial spline basis-set convergence on the angular limits of the He 1s 2 state has been performed. Improvement of algorithm allows reaching the full ci limit in a large radial (79 spline functions) and angular (Imax=80) expansion. A variational energy of - 2.903724299061 au, with an error of 7.8 × 10-8 au is obtained, improving by over two orders of magnitude the previous available limit. Accurate angular momentum limits (1 × 10-8 au) are obtained up to l = 25. Analysis of the behavior of two-particle radial wave functions reveals a sharply peaked behavior which allows effective truncation of the two-electron radial basis for high angular momentum values. A reasonable estimate of computational resources required indicate that an accuracy below 1 × 10-8 au is presently feasible and about 1 × 10-9 au possible in the near future. © 1995 John Wiley & Sons, Inc.
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  • 59
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    International Journal of Quantum Chemistry 56 (1995), S. 153-159 
    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 stopping of energetic ions by ultrathin films is of interest, as such films are mesoscopic structures which comprise the delamination limit of crystals, and as they are of practical interest because of their connection to microelectronics. A matter of special interest is the effect of the number of target layers on the stopping. Here we show that the stopping cross-section, S(N, v), of a system of N layers for projectiles with velocity v is a linear function of N-1 for small N. Such behavior would be expected for N → ∞, in which case the constant term would be the bulk crystalline cross section at the specified projectile velocity and the coefficient of the linear term would be the lowest-order surface correction. Surprisingly, the constant coefficient from a small N fit is reasonably consistent (within limits of imprecision) with the crystalline cross section. This linear scaling of S with N-1 for small N tracks the scaling behavior of the cohesive energy of the films. We discuss the physics and provide some illustrations. © 1995 John Wiley & Sons, Inc.
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  • 60
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    International Journal of Quantum Chemistry 56 (1995) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    International Journal of Quantum Chemistry 56 (1995), S. 333-336 
    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 article, we justify the use of standard Kohn-Sham (KS) band structure theory for the calculation of the low-energy spectrum of metals and the density of states. For the higher spectrum, one can start the KS excited-state calculations by using as the first-order approximation the spin orbitals of the ground state. We next deal with the problem of degenerate states by using the subspace theory minimum principle. © 1995 John Wiley & Sons, Inc.
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  • 62
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    International Journal of Quantum Chemistry 56 (1995), S. 395-410 
    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 detailed derivation of the equations for the energy gradients for excited-state wave functions is presented. These excited states are generated by singles-only CI (CIS) from the Hartree-Fock ground-state wave function. The gradients are obtained from direct differentiation of the CIS energy expression. Since this expression contains explicit terms involving the derivative of the Hartree-Fock orbital coefficients, coupled perturbed Hartree-Fock (CPHF) equations are used to eliminate the need to evaluate these terms. The final equations are then transformed to the atomic orbital basis to avoid costly AO-to-MO transformations. © 1995 John Wiley & Sons, Inc.
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  • 63
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe the design philosophy, structure, and supporting tool kits of the NWChem computational chemistry package. The primary purpose of this effort was to develop efficient parallel algorithms for a broad range of methods commonly used in computational chemistry. To facilitate this, we developed a shared nonuniform access memory model which simplifies parallel programming while at the same time providing for portability across both distributed- and shared-memory machines. In addition to this specific focus on parallelization, a substantial effort has been made to simplify the general problem of large-scale software development, which is common to many research groups. We find that this simplification can be achieved through judicious use of ideas from the computer science field of software engineering in the design and implementation of the program with minimal extra effort on the part of the chemist. © 1995 John Wiley & Sons, Inc.
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  • 64
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    International Journal of Quantum Chemistry 56 (1995), S. 523-531 
    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 dielectric constant of a material is a macroscopic property that measures the reduction of the electrostatic forces between charged plates separated by the material, compared to a vacuum as intermediate material. It is next encountered as a scaling parameter in Coulomb's law for interacting charges, not only in the force, but also in the energy. In deriving the theory for dielectrics, the macroscopic nature is essential: Only then is the basic assumption that the dielectric material is homogeneous and isotropic a valid one. The appearance of the dielectric constant as a simple scaling factor in Coulomb's law has tempted many computational chemists to forget about the macroscopic nature of the dielectric and to apply the screened Coulomb's law between charges, supposedly in a low-dielectric medium such as proteins, in microscopic force fields. Optimization of force fields even led to distance-dependent “dielectric constants.” Another use of the dielectric constant appears in the dielectric continuum reaction field approaches for the computations of solvation energies and solvent effects. The solute is embedded in a cavity surrounded by the dielectric. Specific interactions between solvent molecules and solute are thus neglected. The cavity size and dielectric constants of interior and exterior are optimized for the model. The aim of this article is to show, by means of calculations on interacting point charges embedded in cavities surrounded by dielectrics and microscopic models of “low-dielectric” materials by explicit polarizabilities, that as far as the dielectric “constant” is concerned anything can happen, depending on the nature of the charges, the distance to the cavity boundary, the spatial arrangement of charges, and polarizabilities. Thus, a warning is issued to injudicious use of dielectric models in microscopic calculations. © 1995 John Wiley & Sons, Inc.
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  • 65
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    International Journal of Quantum Chemistry 56 (1995), S. 549-557 
    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 C2v potential energy surfaces for the end-on and side-on approaches of H2 to the rhodium dimer were studied through self-consistent-field (SCF) and multiconfigurational SCF calculations, followed by extensive variational plus second-order multireference Møller-Plesset perturbational configuration interaction (CIPSI) calculations. Relativistic effective core potentials were used to replace the core electrons of the rhodium atoms. Together with the Rh2—H2 interaction, the spectroscopic constants for the 5Σg+, 1Σg+, 3Πu, and 1Πu states of Rh2 are reported. We found that the potential energy curves of the parallel and the perpendicular Rh2(5Σg) interaction with H2 show that the rhodium dimer has the ability to capture and break the H2 molecule. The parallel interaction presents a soft potential barrier of 7.8 kcal/mol, energy necessary to surmount before the capture and breaking of the H—H bond. In the perpendicular interaction, we found that Rh2 captures and breaks spontaneously H2. The potential energy curve of the parallel Rh2(1Σg) + H2 interaction shows that Rh2 also captures and breaks spontaneously the H2, with a very deep well of 92.7 kcal/mol, while in the perpendicular approach, we found that Rh2 has to surmount again a soft barrier of 5.2 kcal/mol to capture and break the H2 molecule. Finally, the energy curves of the parallel (Rh2(1,3Πu) + H2) interactions present capture and breaking with very small barriers. The perpendicular interactions capture and scisse the hydrogen molecule spontaneously. © 1995 John Wiley & Sons, Inc.
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  • 66
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    International Journal of Quantum Chemistry 56 (1995), S. 577-584 
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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 aspects of the fragmentation of the A2Σ+ state of SH via the predissociation and photodissociation processes, SH(A2Σ+, v, N, F1/F2) → S(3PJ) + H(2S) and SH(X2Π, v, N, e/f) → SH(A2Σ+, v, N, F1/F2) → S(3PJ) + H(2S) are considered by ab initio configuration interaction (CI) calculations. All the relevant interstates A2Σ+, X2Π, 14Σ-, 12Σ-, and 14Π spin-orbit induced matrix elements, treated within the full microscopic Breit-Pauli approximation, and Coriolis (electronic orbital angular momentum) couplings are determined based on wavefunctions comprised of 680000-860000 configuration state functions. © 1995 John Wiley & Sons, Inc.
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  • 67
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
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  • 68
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    International Journal of Quantum Chemistry 56 (1995), S. 29-37 
    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 aziridine analogues of the epoxide metabolites of carcinogenic polycyclic aromatic hydrocarbons have greater mutagenic potency than the epoxides. Like their well-studied analogues, the aziridines undergo a pH-dependent decomposition that leads to a reactive carbocation intermediate. In aqueous solution the nucleophile with which the carbocation generally reacts is water. The kinetics of this pH-dependent reaction have been experimentally characterized by others. Although the effect of DNA on this reaction has not been studied, we hypothesize that, like their epoxide analogues, the aziridine derivatives of polycyclic aromatic hydrocarbons undergo a DNA-catalyzed reaction leading through a carbocation to either a DNA-adduct or a hydrolysis product. Using Poisson-Boltzmann calculations in conjunction with Metropolis Monte Carlo simulations and energy-minimized conformations, we predict the DNA-dependence of the acidcatalyzed decomposition of the K-region aziridine, phenanthrene[9,10]imine. © 1995 John Wiley & Sons, Inc.
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  • 69
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    International Journal of Quantum Chemistry 56 (1995), S. 95-102 
    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 present nonlocal density-functional calculations for a model of the [Fe4S4]3+ cluster found in high potential iron proteins, which consists formally of a ferric pair Fe 3+Fe3+ and a mixed-valence pair Fe 2.5+—Fe2.5+. Three Spin Hamiltonian parameters, J (the interlayer Heisenberg interaction), B (a resonance delocalization term) and ΔJ12 (associated with the ferric pair) have been estimated using density-functional energies of a high-spin state as well as two different broken symmetry states. We obtain J=673 cm-1, B=878 cm-1, and Δ J12=160 cm-1. These results are discussed in the light of experimental work on a model compound in the same oxidation state, in which the temperature dependence of the magnetic susceptibility was analyzed with this sort of spin Hamiltonian. Good overall agreement between theory and experiment (J=652 cm-1, B=592 cm-1), and ΔJ12=145 cm-1 is found. In particular, the antiferromagnetic spin coupling constant for the ferric pair exceeds in magnitude all other Heisenberg-type interactions (ΔJ12 〉 0) as expected from previous theoretical and experimental work; this is the first time that the broken symmetry method has been used to analyze a spin Hamiltonian with multiple coupling constants in an Fe4S4 cluster. © 1995 John Wiley & Sons, Inc.
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  • 70
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    International Journal of Quantum Chemistry 56 (1995), S. 137-143 
    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 hydrolytic stability of allylic (IA) and phenolic (IB) esters of novel bifunctional nonpsychotropic cannabinoids, homologs of (+)3S,4S-7-hydroxy-Δ6-tetrahydrocannabinol, is of practical importance due to their possible use as prodrugs. The influence of the bulk and nature of various acyl groups as well as of their position on the base catalyzed hydrolysis has been examined theoretically. Differences (ΔΔHf) between semiempirical heats of formation (ΔHf) of products and reactants were calculated for the formation of the tetrahedral intermediates (IIA, B) which constitutes the rate-determining step of the process. An analysis of the ΔΔHf values and of the calculated optimized lowest energy geometries indicates that formation of II and thus the hydrolysis is most favorable for the trifluoroacetyl and trimethylammoniumacetyl as compared to acetyl, glycyl, and dialkylaminoacetyl esters. The bulk of the acyl group in a series of glycinate esters, increasing in the order COCH2NH2 〈 COCH2NMe2 〈 COCH2NEt2 〈 COCH2N(iPr)2 stabilizes I proportionally, by hindering formation of II. By comparing series IA and IB, the formation of II appears to be generally favored for the phenolic esters compared to the allylic esters due to the release of a more significant steric strain. © 1995 John Wiley & Sons, Inc.
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  • 71
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    International Journal of Quantum Chemistry 56 (1995), S. 221-234 
    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 communication compares three different approaches to the study of ammonia protonation in acidic chabazite: the cluster model, the supercell model, and the embedded cluster model. In all cases, the Hartree-Fock approximation has been adopted, and a minimal Slater-type orbital basis set has been used. To calculate the interaction energies of ammonia by means of the periodic model, the CRYSTAL92 program has been used. The same program has been employed to generate the Madelung field in which a molecular cluster may be embedded. It also provides the reference solution necessary for the embedded cluster model calculations, which in turn have been performed with the EMBED93 program. All three techniques lead to similar interaction energies; however, the embedded cluster approach allows for the most natural way of performing the present adsorption study. Only those atoms which are chemically involved in the interaction have to be treated explicitly, while the rest of the system, though chemically inert, is treated as a consistently described background acting on the adsorption complex. The present investigation suggests that cooperative interaction between molecules trapped in the cavities of zeolites is of crucial importance for the protonation of ammonia to occur. © 1995 John Wiley & Sons, Inc.
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  • 72
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    International Journal of Quantum Chemistry 56 (1995), S. 253-256 
    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 presents some electronic ab initio calculations of ion clusters simulating a piece of alkali halide crystal, both pure and doped with Tl+. In the case of pure crystals, we calculate the (direct) energy band gap from the cluster energy levels. For the case of doped crystals, we calculate the absorption and emission energies and the corresponding Stokes shifts. The cluster model consists of a central cation surrounded by three or four shells of ions, with and without point charges embedding the cluster. © 1995 John Wiley & Sons, Inc.
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  • 73
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    International Journal of Quantum Chemistry 56 (1995), S. 297-301 
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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 approach of Gross, Oliveira, and Kohn for fractionally occupied states of ensembles is applied to determine ensemble exchange potentials for multiplets. A recently proposed method of the author is used to construct exact ensemble exchange potentials of multiplets. © 1995 John Wiley & Sons, Inc.
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  • 74
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    International Journal of Quantum Chemistry 53 (1995), S. 413-418 
    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 helium dimer 4He2 has recently been detected, confirming earlier ab initio predictions of stability for a single bound state with binding energy of 1.310 mK. The predicted potential minimum is at 2.96 Å, with a radial distribution function peaking at 6.96 Å. We model this system using a Dirac bubble potential, which also admits just one bound j = 0 state. With the bubble located at 6.96 Å, an overlap of 0.9994 with the ab initio wave function is obtained. An average internuclear distance of 52.6 Å is calculated, in good agreement with the ab initio result. The root mean square deviation from the mean, 48.0 Å, indicates an enormous spread of the radial wave function. Also consistent with our model is the absence of bound states for the isotopic variants 3He4He and 3He2. Cross sections for helium-helium scattering are also computed, using both a partial-wave expansion and the Born approximation. General trends in the energy dependence of the total cross section are accounted for, in qualitative agreement with experimental results. © 1995 John Wiley & Sons, Inc.
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  • 75
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    International Journal of Quantum Chemistry 54 (1995), S. 223-234 
    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 separation of the dynamic linear response is developed, which distinguishes between the one- and two-electron contributions to the molecular response, by partitioning the RPA equation. The derivation of the partitioning is given in both an RPA, equation of motion, type approach and using the alternative, but equivalent, density matrix method. Three physically distinct contributions are obtained, called the direct, interaction, and back contributions. The direct term is composed entirely of one-electron effects, while the interaction and back terms account for the electron-interaction contributions to the response. Results for the dynamic dipole polarizability suggest that while the one-electron contribution is dominant in the zero-frequency limit, the two-electron contribution becomes increasingly important as the frequency of the perturbation increases. This implies that approximation of the linear response by only one-electron contributions is acceptable for the static case, but is less relevant for the dynamic case. The ramifications of this observation, for the scaling of sum-over-states-type calculations of large molecular systems, is briefly discussed, as is the application of our partitioning method to the higher polarizabilities. © 1995 John Wiley & Sons, Inc.
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  • 76
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    International Journal of Quantum Chemistry 54 (1995), S. 261-263 
    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: Accurate nonrelativistic numerical Hartree-Fock results are reported for the heavy atoms Cs (Z = 55) through Lr (Z = 103) in their ground states. © 1995 John Wiley & Sons, Inc.
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  • 77
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    International Journal of Quantum Chemistry 54 (1995), S. 265-270 
    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 three-dimensional EHMO crystal orbital calculations for crystalline C60, Ca3C60, and Ca5C60 are reported. The ground states of both undoped solid C60 and partially doped Ca3C60 are found to be insulating with an indirect energy gap of 1.2 and 0.5 eV, respectively. In contrast, Ca5C60 forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level, which is found to be located close to a peak of the density of state. The character of crystal orbitals near the Fermi level for both Ca3C60 and Ca5C60 is completely carbonlike. In both cases, the Ca atoms are almost fully ionized and C60 molecules form a stable negative charge state with six to 10 additional electrons. © 1995 John Wiley & Sons, Inc.
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  • 78
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    International Journal of Quantum Chemistry 54 (1995), S. 293-297 
    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: Structures, heats of formation, and vibrational eigenvalues have been calculated by semiempirical AM1 quantum mechanical method for the reactants, products, and activated complexes of three Mannich reactions, namely, the reaction between potential Mannich reagent H2N+ = CH2Cl- and furan and the conventional Mannich reactions between ammonia, formaldehyde, and furan in neutral and acidic media. It has been found that the Mannich reaction involving the potential Mannich reagent occurs more quickly than do the conventional Mannich reactions in neutral medium; the Mannich reaction in acidic medium proceeds most quickly. The results have been discussed in terms of the orbital match and static electric interaction between some atoms of reactant complexes. © 1995 John Wiley & Sons, Inc.
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  • 79
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    International Journal of Quantum Chemistry 53 (1995), S. 37-47 
    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 stepwise acid dissociation constants for p-benzohydroquinone (QH2) in aqueous media have been explicitly calculated for the first time, with the INDO parametrized SCF-MO method. We have optimized the geometries of QH2, QH-, and Q2- and of the QH2 · 6H2O, QH- · (H3O+) · 5H2O, and Q2- · (H3O+)2 · 4H2O systems that model the solvated species. The presence of the associated water molecules (and hydronium ions) account for the stabilization due to hydrogen bonding as well as for a part of the effect of interaction of these molecules with the respective reaction fields in an aqueous medium. To simulate the first solvation shell in a more complete manner, four more water molecules have been considered to be placed above and below the quinonoid ring and the optimized geometries of the resulting hydrated species, QH2 · 10H2O, QH- · (H3O+) · 9H2O, and QH- · (H3O+) · 8H2O, have been determined. The standard free-energy changes calculated for the dissociation of QH2 into QH- and H+ is 0.0251 Hartree (65.9 kJ mol-1) and that of QH- into Q2- and H+ is 0.0285 Hartree (74.8 kJ mol-1). Experimentally observed dissociation constants for these two steps correspond to free-energy changes of 0.0214 Hartree (56.2 kJ mol-1) and 0.0248 Hartree (65.1 kJ mol-1), respectively. © 1995 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 53 (1995), S. 67-76 
    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 consider a crystal as partitioned into a localized molecular cluster (containing a defect or not) and an embedding region. Within the Hartree-Fock formalism, an expression is derived for an effective potential due to the embedding region of crystal. This potential is part of the cluster Fock operator and requires input from a perfect crystal calculation. Special features of the derivative are rigorous inclusion of cluster-embedding overlap and orthogonality between single-electron states of the embedding region and the function-space manifold of the cluster; physically correct normalization of the Fock eigenstates; and a nontrivial total-energy algorithm. Computational requirements are qualitatively compared with those for an isolated cluster. The method allows for intracluster (and intraembedding) correlation and can be adapted straightforwardly to local density functional approaches. Fundamental aspects of the embedding problem are addressed in a general formulation that is, nevertheless, oriented toward explicit calculations. © 1995 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 53 (1995), S. 77-81 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report here the first quantitative theory of the change of anisotropic Fermi surfaces (FS) due to the dynamical e-e interaction. The new FS is constructed as a self-consistent solution of the Dyson equation. This incorporates effects of “anomalous” diagrams, absent in the usual perturbation theory, but which are responsible for changing the FS. Calculations are presented for 2D electrons. Correlations reduce the anisotropy. © 1995 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 53 (1995), S. 95-95 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    International Journal of Quantum Chemistry 53 (1995), S. 97-103 
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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 importance of deductive theories in the modern natural sciences built essentially on experiments is briefly discussed. The logical structure of the deductive theories, their axioms, undefined quantities, and realizations is treated in some detail. In all the natural sciences, there is a striving to explain all the various phenomena in nature in terms of a few basic principles, and this “reductionism” leads to a certain amount of unification of these sciences. The chain that goes from biology, over molecular biology, biochemistry, chemistry, and physics to the description of nature in terms of the elementary particles obeying the laws of modern quantum chemistry is reviewed. Since all the measurements of microcosmos involve an observer, who according to the Copenhagen school experiences the outside universe as a projection on his or her mind through his or her senses, some theoreticians may be inclined to reduce the natural sciences to the human mind as the fundamental (undefined) quantity. However, since the observer is a biological structure, one is also back where one started, and it is evident that one can start the reduction or unification of the natural sciences in any point on this circle (or spiral). Hence, there are many descriptions of the natural sciences and their connections that are possible - as illustrated at this symposium. © 1995 John Wiley & Sons, Inc.
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  • 84
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    International Journal of Quantum Chemistry 53 (1995) 
    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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  • 85
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    International Journal of Quantum Chemistry 53 (1995), S. 275-286 
    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 present here a perturbative analysis of the coupled cluster response method for molecular static properties with Euler and extended coupled cluster functionals under cubic truncation. Comparative analysis is meant to cater to both pedagogical and practical interests. Comprehensive tables for energy-derivative expressions and equations at the stationary point are presented. © 1995 John Wiley & Sons, Inc.
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  • 86
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    International Journal of Quantum Chemistry 55 (1995) 
    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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  • 87
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    International Journal of Quantum Chemistry 55 (1995), S. 237-243 
    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: We discuss the physical nature of nonadditivity in many-particle systems and the methods of calculations of nonadditive contributions to the interaction energy. For neutral clusters, a closed recurrence formula which expresses the energy of m-body interactions through the energies of 2-, 3-, and (m - 1)-body ones is obtained. The general approach for calculation of the nonadditive contribution in the interaction energy of charged systems is developed. The comparative calculation of anionic and neutral silver clusters shows that the geometry of the most stable anionic clusters is established mainly by the additive forces. The stability of neutral silver clusters is determined by the competition of attractive additive forces and repulsive nonadditive ones. © 1995 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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  • 88
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    International Journal of Quantum Chemistry 55 (1995), S. 277-280 
    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 performed CAS-CI calculations on Li2 using a set of molecular orbitals (MO) optimized with a procedure that, in the case of highly symmetric molecules, permits extraction of a small set of MO out of a large set of atomic orbitals (AO). The dimension of the CAS-CI space was of about 12 million symmetry-adapted determinants. We determined some spectroscopic constants of Li2 with three different atomic basis sets of increasing quality. The values obtained with the largest atomic basis set are very close to the experimental results. © 1995 John Wiley & Sons, Inc.
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  • 89
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    International Journal of Quantum Chemistry 55 (1995), S. 281-289 
    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 detailed analysis of the performance of the QDPT CI method, which is based on the application of quasi-degenerate perturbation theory (QDPT) within the configuration interaction (CI) approach, is presented by comparing the QDPT CI results and those obtained from the diagonalization of the perturbative space. Calculations of core and valence excitation and ionization spectra of the CO molecule, which is a strongly correlated system, are carried out using a DZ basis set and the accuracy of the eigenvalues and eigenfunctions is checked through the comparison of excitation and ionization energies and intensities. Excellent agreement is obtained for all values, indicating the computational advantages of QDPT CI which is able to explore wide energy ranges without requiring the diagonalization of large spaces. © 1995 John Wiley & Sons, Inc.
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  • 90
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    International Journal of Quantum Chemistry 55 (1995), S. 347-359 
    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: The extension of the PPP Hamiltonian for alternant cyclic polyenes to noninteger values of the pseudomomentum by imposing modified boundary conditions is discussed in detail. It is shown that a computer program for periodic boundary conditions can be easily adapted to the new boundary conditions. Full CI computations are carried out for some low-lying states of the PPP model of altemant cyclic polyenes (CH)N, (N even) at half-filling. The energy values obtained by using periodic (Bloch) and antiperiodic (Möbius) orbitals are used to perform energy extrapolations for N → ∞. © 1995 John Wiley & Sons, Inc.
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  • 91
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    International Journal of Quantum Chemistry 55 (1995), S. 367-376 
    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
    Notes: General formalism for evaluation of multiparticle integrals involving J̌2 and J̌z operators over explicitly correlated Cartesian Gaussian functions is presented. The integrals are expressed in terms of the general overlap integrals. An explicitly correlated Cartesian Gaussian function is a product of spherical orbital Gaussian functions, powers of the Cartesian coordinates of the particle, and exponential Gaussian factors, which depend on interparticular distances. This development is relevant to both adiabatic and nonadiabatic calculations of energy and properties of multiparticle systems. © 1995 John Wiley & Sons, Inc.
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  • 92
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    International Journal of Quantum Chemistry 55 (1995), S. 393-410 
    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: Ab initio self-consistent-field calculations are reported for electronic states of beryllium clusters comprised of 93, 105, 111, and 123 atoms. The respective clusters correspond to coordination shells 12-15 of a central Be atom with internuclear separations derived from the lattice constants of the bulk metal. Ab initio effective core potentials have been employed to replace the 1 s electrons, thereby reducing the complexity of the calculations. In addition, use of the full D3h point group symmetry of the clusters results in a substantial reduction of the numbers of two-electron integrals that must be computed and processed. Binding energies, orbital energies, electric field gradient, nuclear-electrostatic potential, diamagnetic shielding constant, second moments, and Mulliken populations are calculated for selected electronic states. Calculated binding energies when compared among the different clusters as well as to smaller and larger fragments from earlier studies provide evidence for the onset of convergence to the Hartree-Fock limit of the bulk. Lowest-state ionization potentials are consistently above and agree to within 14% of the experimental workfunction. The net charge on the central beryllium atom decreases toward zero. The variability of observed bulklike behavior for the different properties indicates that the transition between cluster and bulklike behavior is not sharp and depends on the quantity of interest. © 1995 John Wiley & Sons, Inc.
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  • 93
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    International Journal of Quantum Chemistry 53 (1995), S. 83-91 
    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 possibilities and limits of the molecular orbital theory to deal with the problem of determining electronic structure of solids have been explored. A cluster model based on the charge neutrality in the solid has been used in test calculations on some III-V semiconductors and have given quite satisfactory results. Recommendations are given to widen the field of applications of this procedure. © 1995 John Wiley & Sons, Inc.
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  • 94
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    International Journal of Quantum Chemistry 53 (1995), S. 663-677 
    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: This article presents methods for computing matrix elements with Cartesian Gaussian wave functions of potential energy operators that depend on functions of the form (r-r0)n exp[-a(r - r0)] as well as matrix elements of the class of polynomial many-body potentials developed by Murrell et al. The matrix elements arise in the analyses of anharmonic vibrations in molecules. © 1995 John Wiley & Sons, Inc.
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  • 95
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    International Journal of Quantum Chemistry 54 (1995), S. 3-11 
    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: Variational calculations for the lowest-energy states of the hydrogen atom confined in (A) semi-infinite spaces with paraboloidal boundaries, (B) symmetrical boxes with paraboloidal surfaces, and (C) prolate spheroidal boxes were performed with geometry-adapted trial wave functions. Comparisons of variational energies with the exact energies available for the respective geometries provide indications on the reliability of the trial wave functions. This is a necessary and preliminary step to investigate atoms with several electrons in the corresponding confining geometries. © 1995 John Wiley & Sons, Inc.
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  • 96
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    International Journal of Quantum Chemistry 55 (1995), S. 477-484 
    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: Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH3 with Li+, C≡N-, LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C3v) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of association of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. © 1995 John Wiley & Sons, Inc.
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  • 97
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    International Journal of Quantum Chemistry 54 (1995) 
    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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  • 98
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    International Journal of Quantum Chemistry 54 (1995), S. 61-72 
    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 method for solving the problems of spatially confined quantum mechanical systems is proposed. The method works within the framework of the model space approximation. In the case of atoms and molecules trapped into any-shape microscopic cavity (like molecular sieves or fullerenes), the method reduces to a simple modification of the commonly used basis-set quantum chemical calculations. The modification consists of a particular rotation and projection in the model space, leading to solutions better adapted to the boundary conditions of the spatial confinement than the functions that describe the free systems. To illustrate how this method works, it has been applied to the hydrogen atom confined in a spherical well, near a hard wall and confined in a cubic box. The results are also compared to the exact solutions. © 1995 John Wiley & Sons, Inc.
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  • 99
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    International Journal of Quantum Chemistry 54 (1995), S. 93-98 
    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: Molecular structures of neutral and anionic beryllium hydrides have been investigated using ab initio calculations at the MP2 (geometries) and MP4 (energies)/6 - 31++G** levels. ZPE and (if possible) BSSE correction have been included. While BeH2- is not stable, the radical anion of the beryllium hydride dimer is significantly stabilized with respect to the neutral Be2H4 system. Moreover, this anion can appear in two isomeric forms with comparable stability. © 1995 John Wiley & Sons, Inc.
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  • 100
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    International Journal of Quantum Chemistry 54 (1995), S. 107-115 
    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 study the hydrogen atom confined within spherical impenetrable walls. The potential in the box is the Coulombian potential and outside the box the potential is infinite. To compute the energy eigenvalues of the Schrödinger's equation, we use a method proposed few years ago by Campoy and Palma to solve free quantum systems. The energy eigenvalues are computed with great accuracy for different box sizes, in addition we also compute few position expectation values that are related with the hyperfine splitting, nuclear magnetic shielding, polarizability, and pressure. Our results are more accurate than the literature calculations. © 1995 John Wiley & Sons, Inc.
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