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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1702-1705 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new implementation of the complex coordinate method is presented. It is a combination of the stabilization method with the partitioning technique, supplemented with the idea of dilation-adapted basis sets. This method is designed to handle large scale calculations of many-electron resonant states, as to minimize the amount of complex arithmetics and in particular to avoid the diagonalization of the complex eigenvalue problem. Both a resonant eigenvalue and a corresponding eigenvector are obtained. An application to the lowest doubly excited autoionizing states of helium is presented.
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5229-5232 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The 3P, 1D, and 1S states of oxygen and the 4S ground state of the oxygen cation have been studied using large numerical multiconfiguration Hartree–Fock calculations with systematically increased active spaces. The nonrelativistic valence limits for the excitation energies are 1.968 and 4.181 eV for E(3P–1D) and E(3P–1S), respectively. The nonrelativistic valence limit for the ionization potential is 13.593 eV.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 2012-2019 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We derive the nonlinear equations governing vacancy-controlled interdiffusion in a two-component noninteracting lattice gas. We observe that when the diffusion constants of the two species are not equal, the problem cannot be reduced to a simple linear diffusion. In order to treat the strongly nonlinear limit of large kinetic asymmetry and small concentration of vacancies, we introduce an adiabatic approximation in which the "fast'' species is in an equilibrium state defined by the instantaneous distribution of the "slow'' species, which obeys a linear diffusion equation with a renormalized diffusion coefficient. Comparison with numerical solutions of the nonlinear equations shows that the adiabatic approximation captures the essential physics of the diffusion process.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 5927-5938 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Deuterium nuclear magnetic resonance (NMR) spectra are presented for homologues of two series of pyramidic liquid crystals, viz., hexaalkyloxytribenzocyclononatriene, I-n, and hexaalkanoyloxytribenzocyclononatriene, II-n, (where n represents the number of carbon atoms per side chain). The homologues of series I-n exhibit a single hexagonal columnar mesophase PA, while those of series II-n exhibit one or two columnar mesophases (depending on n); a low-temperature biaxial phase PD, and a high-temperature hexagonal phase PC. NMR measurements were performed in the mesophase region on compounds specifically deuterated at the crown methylene groups of the tribenzocyclononatriene core. The spectra in both systems exhibit dynamic features typical of molecules reorienting about their C3 axes within the columnar structures. The experimental spectra were compared with simulated line shapes calculated on the basis of two reorientation mechanisms, (i) symmetric threefold jumps and (ii) planar diffusion about the molecular symmetry axis. It was found that the two compounds of series I-n studied, I-7 and I-10, exhibit spectral line shapes which fit best the planar diffusion model, as was found earlier for the I-8 homologue of this series, while the spectra of the three compounds of series II-n, II-13, II-14, and II-15 are only consistent with the symmetric threefold jump model. Possible reasons for the difference in behavior between the two series are discussed. In an Appendix the asymptotic method for calculating frequency-domain spectra is described.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 6622-6633 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using several simple systems as examples, we show that the choice of optimization functional can have a significant influence on the accuracy of variational Monte Carlo calculations. In addition, we demonstrate that the Monte Carlo analog of the Rayleigh–Ritz procedure, which explicitly orthogonalizes ground and excited states, can be used to produce accurate eigenvalue and variance estimates of excited states.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4230-4235 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground state energies of the helium atom, H2 molecule, and the HeH+ and H+3 molecular ions are calculated, using the variational method and basis sets of explicitly correlated Gaussian-type geminals. These energies are accurate to about 1 μhartree for He and H2 , about 27 μhartrees for HeH+, and an estimated 10 μhartrees for H+3. This accuracy is comparable to that of the Hylleraas-CI method and for diatomics approaches that obtained with explicitly-correlated basis sets in elliptical coordinates.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3074-3085 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The classical Nernst theory for diffusion-limited electrical current transport in electrolytic cells predicts limiting currents of order microamps for unstirred cells. For unstirred cells, one encounters much higher current densities for large enough voltages. In this paper we develop the theory of the hydrodynamic stability of an electrolytic cell as a function of the imposed electric current. A new electrohydrodynamic instability is encountered when the current is forced to exceed the Nernst limit. The convection is driven by the volume force exerted by the electrical field on space charges in the electrolyte. This intrinsic instability is found to be easily masked by extrinsic convection sources such as gravity or stirring. We perform a linear stability analysis and derive a dimensionless number Le whose value determines the convection pattern. The quiescent cell becomes hydrodynamically unstable if (i) the current density exceeds the Nernst limit and if (ii) Le(very-much-greater-than)1. We expect full hydrodynamic convection if Le/Pr(very-much-greater-than)1 with Pr the Prandtl number.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 8407-8414 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We show that the guiding function, which is used to generate the Monte Carlo integration points in a biased-selection calculation, can be optimized so as to minimize the statistical error of an expectation value. For excited states we introduce an orthogonalizing part into the minimization functional to prevent ground and excited states from mixing.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 5939-5945 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A method for calculation of dynamic nuclear magnetic resonance (NMR) line shapes of molecules undergoing reorientation diffusion about a single rotation axis in a symmetric threefold potential is developed using the general theory of Freed. The method is used to calculate deuterium NMR spectra of molecules undergoing reorientational diffusion in a model potential of the form V(cursive-phi)=−V0 cos 3cursive-phi, as a function of the diffusion constant DR, and the potential strength V0. It is found that for V0 smaller than kT the resulting line shapes are very similar to those obtained in a potential-free diffusion. When V0〉kT the uneven distribution of the molecules and the hindering effect of the potential barrier have significant effects on the line shape. In this region two distinct motional effects of the diffusion process are observed: (i) At low DR values molecular diffusion within the potential wells results in averaging of the local distribution and consequently to line narrowing. (ii) At sufficiently high DR values diffusion between the potential wells results in lifetime broadening effects similar to those observed in jump processes. Relations between the diffusion constants and the discrete jump rates are discussed.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1383-1383 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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