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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 910-920 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The detailed calculation of the dynamics of a chemical system is usually not considered due to the size and cost of the computation. It is thus useful to examine various approximation methods. Such methods first need to be tried out on simple systems, like one-dimensional motion. Here two approaches to approximating the solutions of the Schrödinger and von Neumann equations by single time-dependent Gaussians are explored and contrasted, explicitly for one-dimensional barrier penetration. The first approach, in which no tunneling occurs, is local in nature and characterized by an expansion of the equations of motion to second order about the average position of the Gaussian wave packet or about the average position and momentum of the Gaussian Wigner function. This approach was first introduced by Heller [E. J. Heller, J. Chem. Phys. 62, 1544 (1975)]. Here both Heller's approach and a more general truncation method are considered. Indeed tunneling can be incorporated if second-order terms in the quantal von Neumann equation are included. However, the resulting dynamics is unstable for kinetic energies where the exact wavepacket (and Wigner function) splits into nonnegligible parts that represent reflection and transmission. In contrast, the second approach is a global method which is obtained by applying appropriate closure approximations to the equations of motion for the first- and second-order position and momentum expectation values. This method allows tunneling and is stable at all kinetic energies. It is also possible to approximate the global equations in such a way that the local equations are obtained.
    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 94 (1991), S. 2794-2806 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new model is developed for the analysis of muon spin relaxation (μSR) measurements of muonium (Mu) reaction rates with other chemical species. The kinetics component of the model is specifically developed for addition reactions but can be extended to direct reactions. The polarization component of the model assumes that the adduct formed possesses a single, effective spin precession frequency. The complete model is solved to obtain an analytic expression for the μSR signal as a function of time. Both a time-ordered sequence method and a Boltzmann spin equation method give equivalent solutions. These solutions are analyzed under various kinetic conditions. It is concluded that the coefficient controlling the decay of the μSR signal is closely related to the adduct formation rate constant, i.e., the high pressure limit of the apparent bimolecular addition rate constant. In the most favorable case, the decay constant gives the adduct formation rate constant directly at all pressures of buffer gas.
    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 84 (1986), S. 3776-3782 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The amplitudes of the signals in μSR exhibit pressure dependencies which are associated with the stopping dynamics of muonium atoms and diamagnetic muon species observed when muons are thermalized in pure noble gases. To explain this effect, a set of coupled rate equations, with time dependent rates and based upon quantal Boltzmann equations, have been developed to describe the spin dynamics for the thermalization of the two species. These, by definition positive, rates depend upon time through the translational single particle density operators associated with each species. Thus, to exactly solve the spin dynamics, the coupled kinetic Boltzmann equations for the stopping process must also be solved. Furthermore, the rate equations also contain spin dynamics generated by the muonium hyperfine interaction. It is the presence of this hyperfine interaction which leads to the loss of polarization for low pressure gases. The coupled quantal rate equations have been solved for a model of the stopping dynamics in which the rates, taken as square box functions of time, describe the charge exchange regime wherein muonium is both formed and ionized by subsequent collisions. Two post charge exchange extensions of this model are now considered. Following the charge exchange region, in the loss model, it is assumed that the rate of muonium formation is zero while the ionization rate is not. On the other hand, the capture model assumes that the ionization rate is zero while the muonium formation rate is not. Fits are presented to the available data for argon, krypton, xenon and neon. Since argon has both diamagnetic and paramagnetic signals then independent fits to each may be compared. A single set of fitting parameters has been found which describes both signals. This single fit requires a further extension of the models. In particular, a missing fraction must be assumed! The missing fraction model is also required when fits are made to the krypton and xenon data. On the other hand, the fit to the neon data is inconclusive. This is the first suggestion that a missing fraction may exist in the pure noble gases. Such missing fractions have been well established in condensed phases.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 86 (1982), S. 1065-1072 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 32 (1986), S. 527-533 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Muonium (μ + e −) in bulk fused quartz is a unique system in that theμ + spin polarization (in the muonium state) relaxes almost entirely via random anisotropic hyperfine distortions (RAHD). As such, this system provides an excellent test case for a new RAHD spin relaxation theory. This theory is quantitatively compared to static zero field data and the functional characteristics in both the high field and dynamic limits are considered as well.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 18 (1984), S. 697-701 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The effects of the charge exchange process on muon spin dynamics have been investigated using a density operator formalism with special interest placed upon the diamagnetic muon and paramagnetic muonium signals observed after thermalization. In the charge exchange region the dynamics of the spin density operator is assumed to be determined by the muonium hyperfine interaction and by electron capture and loss processes for muons. Analytical expressions are obtained for the amplitudes and phases of the diamagnetic muon and paramagnetic muonium signals as a function of the duration of the charge exchange region,t c, which is inversely proportional to the number density of the moderating gas. The theoretical signals exhibit three features which have, as yet, to be experimentally observed, namely: (i) that the amplitudes associated with the muonium Larmor frequency and with the hyperfine frequency are not, in general, equal, (ii) that all the amplitudes are, in general, damped oscillatory functions oft c (temperature/pressure) and (iii) that phase jumps occur when an amplitude decreases to zero and then increases with falling pressure. Fits to the experimental argon data are discussed in light of the above points.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 29 (1986), S. 1493-1502 
    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: In muon spin rotation (μSR) experiments, where spin-polarized positive muons are stopped in condensed matter, three magnetically distinguishable chemical environments can be observed. That is, the Larmor frequencies associated with diamagnetic environments and two types of paramagnetic environments (muonium and radicals) can be resolved. The chemical identities of the latter two are distinct since their Larmor frequencies are distinct, whereas the chemical identities of the possible diamagnetic species are not determined by the Larmor frequency since chemical shifts can not be resolved in μSR experiments. However, two different diamagnetic species have been observed in experiments performed on mixtures of noble gases. Their distinction arises through different thermal rate constants that lead to “fast” and “slow” relaxing components of the diamagnetic signal. The pressure dependencies of the amplitudes associated with these components are related to the stopping dynamics of muons in noble gas targets. A set of coupled rate equations for muon spin dynamics, based upon quantal Boltzmann equations, have been developed to describe this process in single component gases. This theory is now extended to mixtures. In particular, the dynamics of the muon spin is generated by the muonium hyperfine interaction and by time dependent rate constants for the various chemical species that are assumed to be present, namely, muonium and three diamagnetic species. Radicals have not yet been observed in low pressure gases. The coupled quantal rate equations are solved for two models of the stopping dynamics wherein the rates are taken as square box functions of time.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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