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  • 11
    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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  • 12
    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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  • 13
    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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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 60-67 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Nascent CD3 radicals produced by photodissociation of CD3I after absorption of 266 nm radiation by the A˜ state are studied using the photofragment imaging technique. Two-photon, resonance-enhanced, multiphoton ionization [(2+1) REMPI] probes CD3 via the 3pz 2A'2 Rydberg excited electronic state. CD3I photodissociation at 266 nm is found to produce ground-electronic-state CD3 radicals with substantial vibrational excitation of the ν2 umbrella mode. Rotational constants are determined for v=0, 1, and 2 of ν2 in the 3pz excited state by analysis of the spectra. A first-order perturbation and diagonalization procedure is used to generate potential energy curves for the umbrella mode in both the ground and excited electronic states and Franck–Condon factors for various transitions between the states. These results should prove useful when employing REMPI to characterize methyl radicals in many environments.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 3248-3257 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a molecular model for studying the prototypical ferric–ferrous electron transfer process in liquid water, and we discuss its structural implications. Treatment of the nonequilibrium dynamics will be the subject of future work. The elementary constituents in the model are classical water molecules, classical ferric ions (i.e., Fe3+ particles), and a quantal electron. Pair potentials and pseudopotentials describing the interactions between these constituents are presented. These interactions lead to ligand structures of the ferric and ferrous ions that are in good agreement with those observed in nature. The validity of the tight binding model is examined. With umbrella sampling, we have computed the diabatic free energy of activation for electron transfer. The number obtained, roughly 20 kcal/mol, is in reasonable accord with the aqueous ferric–ferrous transfer activation energy of about 15 to 20 kcal/mol estimated from experiment. The Marcus relation for intersecting parabolic diabatic free energy surfaces is found to be quantitatively accurate in our model. Due to its significance to future dynamical studies, we have computed the tunnel splitting for our model in the absence of water molecules. Its value is about 1 kB T at room temperature for ferrous–ferric separations around 5.5 A(ring). This indicates that the dynamics of the electron transfer are complex involving both classical adiabatic dynamics and quantal nonadiabatic transitions. The dynamics may also be complicated due to glassy behavior of tightly bound ligand water molecules. We discuss this glassy behavior and also describe contributions to the solvation energetics from water molecules in different solvation shells. Finally, the energetics associated with truncating long ranged forces is discussed and analyzed.
    Type of Medium: Electronic Resource
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  • 16
    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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  • 17
    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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  • 18
    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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  • 19
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 7749-7760 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We describe a procedure for computing the thermal rate constants for infrequent events that occur in complicated quantum mechanical systems. Following the ideas of Gillan, the procedure focuses on the equilibrium statistics of the centroids for the imaginary time quantum paths. We argue that the imaginary time statistics can be used to efficiently bias Monte Carlo sampling of the real time reaction dynamics. Consideration of imaginary time paths or equilibrium statistics alone leads to a quantum transition state theory. Analytical versions of this transition state theory are developed with the aid of a variational principle. Numerical applications of the quantum transition state theory are given for the one-dimensional Eckart barrier problem and for the nonseparable two-dimensional collinear H2+H reaction. Remarkably accurate results are obtained. The quantum transition state theory we describe provides a rigorous basis and generalizes algorithms recently employed to treat electron transfer and also ionization in polar media.
    Type of Medium: Electronic Resource
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  • 20
    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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