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  • 1
    ISSN: 1520-4804
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 8516-8523 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground state potential energy hypersurface of the GaOH–HGaO system has been investigated using high level ab initio molecular electronic structure theory. The geometries and physical properties of two equilibrium structures, one isomerization transition state and one inversion transition state were determined at the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory with four sets of basis functions. It has been found that freezing the 3d electrons of the Ga atom in the correlation procedures is not appropriate for this system. For the energy difference ΔE (GaOH–HGaO) the freezing of the 3d electrons results in an error of 25 kcal/mol! The dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities are predicted for the four stationary points. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum and diffuse functions [TZ2P(f,d)+diff] basis set, the bent GaOH was found to be 41.9 kcal/mol more stable than the linear HGaO species; with the zero-point vibrational energy (ZPVE) correction, the energy separation becomes 40.4 kcal/mol. The classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGaO→GaOH is determined to be 44.5 kcal/mol and the barrier height with the ZPVE correction 42.3 kcal/mol. The classical barrier to linearity for the bent GaOH molecule is determined to be 1.7 kcal/mol and the barrier height with the ZPVE correction to be 1.2 kcal/mol. The predicted dipole moments of GaOH and HGaO are 1.41 and 4.45 Debye, respectively. The effects of electron correlation reduce the dipole moment of HGaO by the sizable amount of 1.2 Debye. The two equilibrium species may be suitable for microwave spectroscopic investigation. Furthermore, they may also be detectable by IR techniques due to the relatively large intensities of their vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HXO–XOH systems, where X is a group IIIA atom and the HXO+–XOH+ systems, where X is a group IVA atom. © 1996 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 1280-1287 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio electronic structure theory has been employed in order to investigate the ground state potential energy hypersurfaces of the HBO–BOH system. Geometries, dipole moments, harmonic vibrational frequencies, and infrared intensities of two equilibrium and two transition state [inversion (bending through linear geometry) and isomerization] structures were determined at the self-consistent-field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory using three basis sets. The theoretically predicted geometries and physical properties agree very well with available experimental values. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum function [TZ2P(f,d)] basis set, the linear HBO molecule is predicted to be 45.0 kcal/mol more stable relative to the bent BOH species; with the zero-point vibrational energy (ZPVE) correction this energy separation becomes 44.4 kcal/mol; the classical barrier height for the inversion motion of the bent BOH molecule is predicted to be 3.5 kcal/mol and the barrier height with the ZPVE correction is 3.0 kcal/mol; the classical activation energy for the isomerization (1,2 hydrogen shift) reaction BOH→HBO is determined to be 29.4 kcal/mol and the activation energy with the ZPVE correction is 26.6 kcal/mol. © 1995 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 3006-3017 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A study of first and second derivatives of the orbital, electronic, nuclear, and total energies for closed-shell self-consistent-field (SCF) wave functions has been applied to the ground state HBO–BOH and AlOH–HAlO potential energy hypersurfaces. At the stationary points, these energy derivative quantities are uniquely transformed from the Cartesian to the normal coordinate system. Using the four equilibrium and four transition state structures on the two potential energy hypersurfaces, it is demonstrated that the energy derivative method may be used as a powerful quantitative model in understanding and interpreting various chemical phenomena including structures and reactivities. Specifically, the inversion (bending through linear geometry) motions for the bent BOH and AlOH molecules are found to be electronically favorable processes. The isomerization reaction between the linear HBO and bent BOH is seen to be electronically unfavorable, whereas the corresponding reaction between the bent AlOH and linear HAlO is observed to be an electronically favorable process.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 7975-7982 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground state potential energy hypersurface of the GeOH+–HGeO+ system has been investigated employing ab initio electronic structure theory. First, geometries of two equilibrium and isomerization (1,2 hydrogen shift) reaction transition state were determined at the self-consistent-field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory using four basis sets. A qualitatively incorrect geometry is predicted for GeOH+ unless f functions are included in the basis set. Second, physical properties including dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities of three stationary points were evaluated at the optimized geometries. The effects of electron correlation reduce the dipole moment of HGeO+ by 1.25 Debye. At the highest level of theory employed in this study, CCSD(T) using the triple zeta plus double polarization with diffuse and higher angular momentum functions [TZ2P(f,d)+diff] basis set, linear GeOH+ is predicted to be more stable than linear HGeO+ by 71.7 kcal/mol. After correction for zero-point vibrational energies (ZPVEs), this energy difference becomes 70.3 kcal/mol. With the same method the classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGeO+→GeOH+ is determined to be 30.3 kcal/mol and the activation energy (with the ZPVE correction) is 28.0 kcal/mol. The predicted dipole moments of GeOH+ and HGeO+ are 0.61 and 4.64 Debye, respectively. Thus, the HGeO+ ion may be suitable for a microwave spectroscopic investigation. On the other hand, the GeOH+ ion may be suitable for an IR spectroscopic study due to the strong IR intensities of the three vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HCO+–COH+ and SiOH+–HSiO+ systems. © 1995 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Biochemistry 9 (1970), S. 4448-4453 
    ISSN: 1520-4995
    Source: ACS Legacy Archives
    Topics: Biology , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Biochemistry 5 (1966), S. 1805-1814 
    ISSN: 1520-4995
    Source: ACS Legacy Archives
    Topics: Biology , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 65 (1989), S. 3425-3429 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The thermochemical heat of ablation of carbon, HA, is usually set equal to 32 kJ/g as derived from the JANAF tables. There is, however, some uncertainty since JANAF-recommended values for heats of vaporization and partial vapor pressures differ from the results of a detailed analysis that was carried out at the Lawrence Livermore National Laboratory (LLNL). We find that the LLNL model yields carbon-vaporization enthalpies that are appreciably lower than the JANAF-based values. In this light, we examine experimental data generated in the course of a comprehensive investigation of laser-interaction effects in graphite and conclude that our experiments are indicative of an HA equal to 31.0±1.6 kJ/g.
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 87 (2000), S. 2265-2272 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Solid structures consisting of layers of different materials created at elevated temperatures usually exhibit substantial residual stresses. These stresses are caused by intrinsic strains in addition to thermal strains, and originate from the bonding of the layers, which generates internal forces and moments that must be balanced to achieve mechanical equilibrium. It is shown that the solution proposed by Townsend et al. [P. Townsend, D. Barnett, and T. Brunner, J. Appl. Phys. 62, 4438 (1987)] for describing elastic interactions in multilayered, elastically isotropic structures provides a powerful tool for evaluating the strains, the normal stresses off the edges, and the curvature of chemically vapor-deposited (CVD) laminates. The residual stresses acting in each layer are best expressed as follows: σi(z)=Ei′[(εi,0−ε0)+(zN−z)K], where z measures the distance from the bottom surface, Ei′ is the biaxial modulus of the layer, (εi,0−ε0) characterizes the strain mismatch prior to any mechanical relaxation, and (zN−z)K defines the bending contribution, which depends linearly on the distance from the neutral plane and stems from the curvature K. For bilayered structures the curvature can be expressed in a relatively simple form. In conjunction with the proper expression for the average stress in the coating, it is seen that Stoney's equation holds for thickness ratios much larger than expected in the context of the thin-film approximation. The case of CVD laminates made of ZnS on ZnSe illustrates how the theory can be applied for designing structures that minimize the deformation and, thus, for obtaining optically desirable configurations. The stresses acting in bilayered ZnS/ZnSe structures are controlled by the strain differential Δε0=εcintr.+(αc−αs)ΔT, where εcintr. represents the intrinsic strain of the ZnS coating, and (αc−αs)ΔT defines the contribution originating from the thermal expansion mismatch. For ZnS deposited at 670 °C, measurements of the curvature yield Δε0(similar, equals)−5.53×10−4; upon evaluating available information on the thermal expansion of ZnS and ZnSe we conclude that the intrinsic strain of CVD ZnS is compressive and amounts to about 1 or 2×10−4, for thicknesses ranging from 1 to 4 mm. © 2000 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 88 (2000), S. 5487-5489 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Stoney's equation has been—and still is—extensively used to evaluate the macrostress acting in a coating deposited on a thick substrate. In principle, the formula applies only in the "thin-film approximation," that is, for coatings much thinner than the substrate. The main purpose of this communication is to demonstrate that, based on a general theory of elastic interactions in multilayer laminates, the correct formula for the stress can be expressed in terms of Stoney's equation and a correction factor equal to (1+γ δ3)/(1+δ), where γ designates the ratio of the biaxial moduli and δ is the ratio of the layer thicknesses. In this light, it is shown that (a) Stoney's equation does not cause serious errors for thickness ratios δ≤0.1; (b) Atkinson's recently proposed modification, which does not require information on the coating's modulus, yields much improved results for thickness ratios up to δ(similar, equals)0.4; and (c) Brenner–Senderoff-type expressions can be very misleading and should be avoided. © 2000 American Institute of Physics.
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