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  • Computational Chemistry and Molecular Modeling  (6)
  • Biochemistry  (4)
  • free volume  (2)
  • Wiley-Blackwell  (9)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Peptide Science 2 (1996), S. 364-370 
    ISSN: 1075-2617
    Keywords: conformation ; glutamine ; folding ; simulation ; Chemistry ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational preferences of the methylenic sequence in the side chain of the glutamine residue were investigated by ab initio and semi-empirical quantum mechanical calculations and examination of both the Brookhaven Protein Databank and Cambridge Structural Data Base. The results were analysed on the basis of our previous findings about the folding of methylene groups in aliphatic segments. Both energy calculations and the crystallographic structure of small peptides indicate that methylene units of the glutamine residue tend to fold in a gauche conformation. In contrast, such groups usually adopt an all-trans conformation in proteins due basically to the entropic and solvent contributions. These results have been demonstrated by computing the entropic correction to the free energy and evaluating the solvent effects through SCRF calculations
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 52 (1994), S. 947-956 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied symmetry breaking in three open-shell systems: CF4+ (D2d and C2v) and CF32+ (D3h) molecular ions. These different Hartree-Fock solutions are employed as starting points to calculate the correlation energy of these ions with perturbative, configuration interaction, and density functional methods. When symmetry-broken or symmetry-adapted wave functions are used, the correlation energy obtained with each method changes the order of stability of CF4+ for a determined symmetry. Density functional methods produce higher correlation energies although they do not alter the order of stability of Hartree-Fock calculations. The behavior of correlation energy with different methods and the characteristics of the symmetry of wave functions are compared. A study of appearance energies for three different channels of the decomposition reaction of ionized carbon tetrafluoride are considered by using different methods with symmetry-broken or symmetry-adapted wave functions to calculate correlation energies. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 51 (1994), S. 397-405 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Slater-type orbitals (STOs) with a single-exponent by shell or by subshell have been constructed to reduce the number of integrals evaluated in the electronic calculations. The expansion of orbitals in these new basis sets has been carried out in detail for the ground state of the Ne atom. We have carried out a study of STO basis sets with a different size for this atom that could help to propose empirical rules for the selection of these basis sets for other atoms. The usefulness of STOs with single-exponent by shell and subshell and the splitting of s and p functions are discussed. © 1994 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 47 (1993), S. 85-100 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Expansions of STO orbitals with GTOs for the first-row atoms have been obtained by the method of the distance between subspaces. The expansion coefficients and exponential parameters were simultaneously varied when the distance between subspaces, which are generated from STO and GTO functions, is minimized. The ζ; exponents (or scale factors) for the atomic orbitals that are optimized for these atoms are also shown to be almost independent of the number of Gaussian functions. Comparisons carried out with Stewart's least-squares method produce equivalent results when exponents for 2s and 2p functions are different. Some examples and applications for several atomic properties of the first-row atoms are included: energies and expectation values of ri and pi for the several expansions. These new minimal basis sets were tested for diatomic and polyatomic molecules containing these atoms. © 1993 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 991-1004 
    ISSN: 0887-6266
    Keywords: Gas permeation ; polycarbonate ; free volume ; sorption ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas transport properties of semicrystalline films of poly(2,2,4,4-tetramethyl cyclobutane carbonate) (TMCBPC) were studied. Permeability coefficients for He, O2, N2, CH4, and CO2 at 35°C for pressures between 1 and 20 atm are reported as well as sorption isotherms for N2, CH4, and CO2 at the same conditions. The permeability coefficients for TMCBPC are larger than corresponding values for the aromatic bisphenol-A polycarbonate (PC) and tetramethyl bisphenol-A polycarbonate (TMPC), even though the TMCBPC films are semicrystalline. These results are explained on the basis of the larger free volume available for permeation in this polymer. Significant TMCBPC plasticization by CO2 was also observed and this causes typical time-dependent behavior. The plasticization process starts at very low pressures compared with the behavior of aromatic polycarbonates PC and TMPC. This early onset of plasticization seems to be related also to the larger free volume in the amorphous phase of TMCBPC which favors high gas sorption. The diffusion coefficients for TMCBPC are also larger than those reported for the aromatic polycarbonates PC and TMPC. Ideal gas separation factors were found to follow the usual trend; that is, as permeability increases, the ideal separation factor decreases. © 1993 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1577-1589 
    ISSN: 0887-6266
    Keywords: polyphenylene ethers ; gas permeation ; gas sorption ; free volume ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas transport properties of the polyphenylene ethers poly(2,6-dimethyl-1,4-phenylene oxide)PDMPO, and poly(2,6-diphenyl-1,4-phenylene oxide), PDPPO, and the thioether poly(1,4-phenylene sulfide), PPS, have been measured as a function of pressure and temperature. The PPS material and free volume correlations were used to estimate the behavior of the unavailable poly(1,4-phenylene oxide), PPO. The results show that symmetrical substitution of phenyl groups on the backbone of polyphenylene ether, PDPPO, increases the gas transport properties by one order of magnitude relative to the unsubstituted material, PPO. Symmetrical methyl substitution, PDMPO, however, increase the permeability, apparent diffusion and sorption coefficients even further. The gas transport coefficients correlate with the fractional free volume of the polymers. PDMPO has the largest fractional free volume and gas transport coefficients followed by PDPPO and the PPS. The results show that substitution of phenyl groups, which leads to polymers that have better thermal and oxidative stability than methyl substituted ones, can be a useful means for increasing free volume and gas permeability coefficients. While methyl groups appear to be more effective for the latter, the enhanced chemical stability of phenyl rings may be useful when gas separation membranes are to be used in harsh environments. © 1993 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 4 (1983), S. 33-40 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: We present a new procedure for direct minimization of the RHF energy, which presents advantages over SCF methods with respect to convergence rate and computational cost. In this procedure we combine several techniques with the aim of obtaining best directions and step lengths for the iterative search for a minimum of the energy. In this article we develop the theory. Therefore, we analyze the variational function; we present a short description of the minimization techniques and we discuss in detail the way in which they are to be used. The computational aspects of the procedure will be treated in the following article.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 201-207 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A direct minimization method previously presented by the authors is applied here to biconfigurational wave functions. A very moderate increasing in the time by iteration with respect to the one-determinant calculation and good convergence properties have been found. So qualitatively correct studies on singlet systems with strong biradical character can be performed with a cost similar to that required by Hartree-Fock calculations.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 12 (1991), S. 1172-1181 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Slater type orbital (STO) basis sets for the atoms Sc-Zn have been derived using a technique based on the distance between subspaces. The accuracy for several properties of these basis sets has been tested. Basis sets studied are of both single- and double-zeta sizes, although this technique can be generalized for any size. Uniform quality criteria through the series of atoms Sc-Zn are difficulty to establish due to the varying number of d electrons. A comparative study at the atomic level of the quality of STO basis sets (both the two new basis sets and Clementi's basis sets) for the first-row transition elements has been carried out. Results show that the new basis sets provide better simulation for several properties. Molecular calculations on compounds with these atoms using a Gaussian expansion fitted according to the new values of optimized STOs are also included. The results obtained are similar to those reported when STO-3G basis set is used.
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