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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 12310-12314 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 100 (1994), S. 1528-1541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider the diffusion of ionic species in technologically relevant materials such as zeolites. These materials are characterized by a disordered density distribution of charged sites that couple with the diffusing species. We present a model for ion diffusion in a specific form of charged disorder. This is a primitive model for ion diffusion in charged or acidic zeolites. The theory relies on a path integral representation of the propagator, and a Gaussian field theory for the effects of the disorder. We use the Feynman–Bogoliubov variational method to treat the model, and calculate the diffusion coefficient for ions in a medium characterized by randomly located charges. Numerical solution of our equations, and asymptotic analyses of the same, show that in our theory there is a crossover from diffusive to subdiffusive behavior beyond a threshold value for the average density of the disorder. This threshold coincides with the actual diffusion changing from processes well approximated by Gaussian paths to those involving escapes from deep potential wells and barrier crossings. These results are discussed in the context of recent field-theoretic and renormalization group approaches to the problem of diffusion in random media. Our approach to diffusion in random media appears reasonably general and should be applicable to many technologically relevant problems, and is not compute intensive.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 6836-6847 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structure of liquid dimethylsulphoxide (DMSO) at 25 °C is explored using a combination of neutron diffraction with isotope substitution and computer simulation techniques. The potentials used in the computer simulation consist of Coulomb and 6-12 Lennard-Jones interactions for each of the carbon, oxygen, and sulfur sites on the molecule. To interpret the neutron diffraction data most effectively, it is necessary to refine both the molecular internal structure and the intermolecular contributions to the measured structure factors at the same time in order to separate the intermolecular terms correctly, because there is a large degree of overlap between intramolecular and intermolecular distances. This renders the data far more sensitive to the intermolecular forces than if this analysis were not performed. Direct comparison of neutron diffraction data and computer simulation results indicates that existing models of the molecular force field give a sensible description of the liquid structure, although there are some discrepancies which are not fully understood at this time. The question of whether this material can be regarded as an associated liquid, as it is frequently referred to, is discussed. All tests for association that have so far been applied to both the diffraction data and the computer simulation results do not indicate a highly ordered molecular association in the liquid.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5843-5856 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have applied photofragment ion imaging to investigate the dissociation dynamics of low-lying, doubly excited states of molecular hydrogen. A doubly excited electronic state is one in which both of the hydrogen electrons reside in excited molecular orbitals. Two-step, two-color multiphoton excitation of H2, first via 201.8 nm, two-photon excitation into the E, F 1Σ+g(vE=0, J=1) state, followed by ∼563 nm, 1+m (m=1, 2) excitation through the B‘ 1Σ+u(v=0, J=0, 2), D 1Πu(v=2, J=1, 2), and B' 1Σ+u(v=4, J=0, 2) states provides a ready means of populating several low-lying doubly excited states of H2 at increasing internuclear separations. From these doubly excited repulsive states, both dissociation and autoionization processes are possible. Because the excitation energy remains relatively constant as each intermediate state is accessed, differences in the photodissociation dynamics via each state can be ascribed directly to the effects of changing internuclear separation and electronic symmetry of the intermediate and dissociative states. H+ fragments detected from each photodissociation pathway are distinguished by their differing velocities, determined from an ion image.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4672-4675 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The bimolecular abstraction reaction H+HI→H2+I has been investigated in a neat molecular beam of HI using ion imaging to detect the H2 (v=1,J=11,13) products. Images obtained determine the laboratory-frame product velocity distribution and show evidence for reaction with fast and slow H atoms arising from the I (2P3/2) and I*(2P1/2) channels in the photolysis of HI, as well as formation of I and I* in the reaction product channel.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 4444-4453 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have extended the reference interaction site model (RISM)-polaron theory of Chandler et al. [J. Chem. Phys. 81, 1975 (1984)] to treat self-trapping and localized states of excess electrons in polar fluids. The extension is based on a new closure of the RISM equation presented herein. The theory is applied to the hydrated electron employing a simple class of electron-water pseudopotentials. Included in this class are models coinciding with those already examined by others using computer simulations. In those cases, the results for both structural and energetic properties compare well with those of simulation. The work function, or equivalently, the excess chemical potential of the hydrated electron are also computed; the theoretical result agrees with experiment to about 1%. Most interesting, however, is that as the parameter characterizing the pseudopotentials is varied, a critical parameter is found where the electron behavior changes essentially discontinuously from a trapped state to a "super''-trapped state. This transition may have a direct bearing on theoretical efforts to explain the properties of solvated electrons.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 6578-6584 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Acetylene cooled in a He supersonic expansion is photodissociated by excitation in the 201–216 nm region of the A˜ 1Au −X˜ 1∑+g transition. Subsequent ionization of the H-atom fragments by 2+1 (243 nm) REMPI, and mass-selected ion imaging allows analysis of the velocity distribution of H-atoms from the HCCH hν→ C2H+H process. Measurement of the maximum velocity for H atoms from this channel produced by photodissociation of acetylene through the A˜ 1Au −X˜ 1∑+g V70K10, 110V40K10, 210V50K10 and V50K10 vibronic transitions gives a value for D00 (HCC–H) of 131±1 kcal/mol. Other channels producing hydrogen atoms (including HC2 hν→ C2+H and HCCHhν→ HCCH+ hν→ C2H++H) are detected at all photon fluxes used. These multiphoton channels produce hydrogen atoms with higher translational energy and therefore obscure measurement of the maximum velocity of H atoms produced by single-photon dissociation of acetylene. Reduction of photon flux by more than two orders of magnitude to ∼5×106 J/cm2 gives a background, multiphoton, H-atom intensity of ≤7% of the peak primary dissociation intensity. Because this multiphoton background limits the detectability of fast H atoms from single-photon dissociation of acetylene, the dissociation energy reported here is an upper limit. Calculations of potential rovibronic excitation of the C2H fragment are discussed.
    Type of Medium: Electronic Resource
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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. 707-710 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new excited−state spectroscopic method is reported.It is a two−color laser−induced grating tecnique for detecting optical transitions of rovibronically excited molecules in the gas phase. (AIP)
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 835-841 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have performed Monte Carlo calculations for two-dimensional freely jointed polymers with no excluded volume in equilibrium with a quenched random lattice of obstacles. In addition to the obstacle density, there are two microscopic parameters in the problem: the obstacle side length a and the polymer step length l. Our Monte Carlo calculations extend to N=50 000 monomer polymer units. The calculations begin to exhibit standard Flory–Lifshitz scaling only at extremely large values of N. For example, when l≈a, nonuniversal behavior is found for N〈104. For some choices of parameters, this behavior includes a nonmonotonic mean-square end-to-end length R2 as a function of N. These calculations are made feasible by exploiting an equivalence between annealed and quenched disorder valid when the polymer may equilibrate to the quenched material.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 889-894 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We examine path-integral methods for computing electronic coupling matrix elements relevant to long-ranged electron transfer. Formulas are derived that generalize those already found in the literature. These extensions allow for efficient computation, especially for complex systems where there is either no inherent symmetry, or that symmetry is difficult to ascertain a priori. The usefulness of the computational methods based on these formulas is demonstrated by carrying out calculations for the ferrous–ferric exchange.
    Type of Medium: Electronic Resource
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