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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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: Binding of Zn2+ to imidazole (Im) and methyl imidazole (MeIm) is studied by ab initio methods as a model for the effect of cation binding on tautomeric energies. Gradient energy optimized conformations were obtained for all neutral and ionic structures, including the deprotonated molecules and the ylides. The N3—H tautomer of MeIm is calculated to be more stable than N1—H by about 1 kcal/mole. However, binding of a Zn2+ cation to the available nitrogen site is found to reverse the order of binding, leaving N1—H more stable by 1 kcal/mole. Binding of Zn2+ produces a significant perturbation in the electronic structure, a smaller shift in the equilibrium conformation of the imidazole ring, and only a small absolute shift in the relative tautomer energies. Methyl substitution at C5 has a small effect on both conformation and energetics.A high-energy ylide tautomer is produced by moving the proton bound to C2 to the N1 atom. The binding of Zn2+ to the C2 site is substantially stronger than to the N1 site, yielding nearly isoenergetic ZnIm2+ conformations for binding to either N or C atoms. For the deprotonated salts the lowest energy conformation has the C2—N3 bond bridged by Zn2+.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 4 (1983), S. 127-135 
    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 relativistic effective core potential (REP) has been generated for the uranium atom and used in self-consistent-field calculations of the A states of UH, UF, and their ions. Energy curves were calculated at the base configuration level which ensures the dissociating atoms are described by Hartree-Fock wavefunctions. The electronic bonding of these molecules is found to be similar to that of comparable alkaline-earth hydrides and fluorides. The uranium 6p, 6d, and 5f orbitals retain their atomic character but the orbitals extend into the bonding region and are distorted by overlap repulsion and electrostatic effects. Nonetheless, the atomic energetic coupling determines that low energy states will have the maximum spin multiplicity and maximum orbital angular momentum projection consonant with the charge-transfer bonding.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 6 (1985), S. 287-295 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Relativistic effective potentials (REP) are now widely used in molecular electronic structure calculations. Tests of these REP are needed to assess their accuracy. This can now be done for AgH and AuH since Lee and McLean have published Dirac-Fock calculations for these molecules. Comparative SCF calculations have been performed for two types of effective potential. Satisfactory agreement between the effective potential results and Dirac-Fock values is found for spectroscopic constants and dipole moments, which supports the use of these potentials for heavy atom containing molecules.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 3 (1982), S. 372-380 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Spin-orbit and dispersion energy contributions to the energy curves of XeF are examined. A rapid variation in the spin-orbit coupling with internuclear separation is found for both the ground and excited states. This result can explain the experimentally observed ordering of the ionic excited states when the spin-orbit perturbation couples 2σ and 2π energy curves obtained by both all-electron and effective core potential (ECP) calculations at the first-order configuration interaction (FOCI) level of accuracy. Damped dispersion energy contributions to the ground-state energy curve are shown to be comparable to the charge transfer contribution. The energy curve for XeF is in reasonable agreement with experimental results and a calculation of the analogous XeCl curve confirms the qualitative correctness of the calculation. The energy curves and transition moments were then applied to two problems related to the efficiency of the XeF laser. Photodissociation of the X state provides a means of removing a bottlenecked vibrational level but a calculation of the radiative transition probability between the X and A states finds the cross section is too small to yield rates competitive with collisional deactivation. The bottlenecked state may also be removed by electron dissociative attachment but the calculated energy curves for the X states of XeF and XeF- do not cross at a low energy indicating a small cross section.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 42 (1992), S. 1469-1477 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical models of divalent cobalt bound to the active site of the enzyme, carbonic anhydrase, are constructed to study the effect of the first-shell geometry and coordination number on the experimentally observed visible spectra. Favorable comparisons of the ab initio calculations of the hexa-aquo complex of Co(II) with experimental results provides a test of the method. The d-d spectra variation with pH in the enzyme is found to be determined by the first-shell complex geometry as obtained from energy optimization. The low pH complex is predicted to be predominantly five-coordinate with two waters in the first-shell, whereas the high pH complex is predominantly four-coordinate. Equilibria between the four- and five-coordinate structures at low pH is not indicated by the calculation.
    Additional Material: 5 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0020-7608
    Keywords: ab initio excitation energy ; five-coordinate vanadate ; ribonuclease active site ; effective fragment potential ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Knowledge of the ionicity of the phosphorane intermediate is important to the analysis of the microscopic mechanism of the hydrolysis of the phosphate ester bond by ribonuclease A (RNase A). Five-coordinate uridine vanadate, an analog of the phosphorane, binds to RNase A as the monoanion. The absorption spectra of the vanadate is a probe of the electronic structure of the active site. An in vacuo theoretical model of H4VO5- is calculated to have transitions only in the far ultraviolet (UV). However, H2VO5C2H4- has one in the near UV as well as others further into the UV. The transition energy of the monoanion calculated in the field of the protein active site with effective fragment potentials shifts modestly to the red. Broad monoanion absorptions are predicted which would overlap an observed incomplete very broad absorption attributed to the complex of uridine vanadate with RNase A. The absorption bands of neutral ethylene glycol vanadate are predicted to be further to the red but also overlap the experimental absorption.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 11-19, 1998
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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