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  • 1
    ISSN: 1520-6904
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 75 (1971), S. 1492-1501 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of organic chemistry 56 (1991), S. 5459-5462 
    ISSN: 1520-6904
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 73 (1993), S. 8386-8396 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: We have measured room-temperature band-to-band recombination decay kinetics in superior quality GaAs heterostructures, and have observed the longest lifetime (2.5 μs) observed for any GaAs/AlxGa1−xAs structure to date. Additionally, using a novel time-resolved optical photoluminescence imagining technique, analogous to the Haynes–Shockley experiment, we have also measured room-temperature minority-carrier transport in this series of "surface-free'' GaAs/Al0.3Ga0.7As double heterostructures, measurements only possible in high-quality samples with long lifetimes and intense photoluminescence. We find the transport to be diffusive with diffusion lengths of (approximately-greater-than)100 μm. Further, we find, for thick structures, minority-carrier transport is hole-dominated ambipolar diffusion, as expected for high-purity n-type material. However, for thinner structures, we find that the minority-carrier transport is time dependent, changing from ambipolar diffusion at early times, as in thick structures, to electron-dominated diffusion at later times. We show that these structures become effectively p-type modulation doped due to the relative "impurity'' and thickness of the AlxGa1−xAs compared to the GaAs. As a result, the minority-carrier species changes from holes to electrons for decreasing GaAs layer thicknesses. Cumulatively, we show the band-to-band recombination decay kinetics and carrier transport results to be in excellent qualitative and quantitative agreement. Moreover, our results are in excellent agreement with electrical transport measurements of electron and hole mobilities. Finally, with our measured room-temperature lifetimes and minority-carrier transport measurements versus GaAs layer thickness, we accurately calculate the interface recombination velocity for these structures, with the result S∼40 cm/s, among the lowest ever reported for any GaAs/AlxGa1−xAs structure.
    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 98 (1993), S. 8704-8709 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio molecular electronic structure theory has been used to study the AlOH–HAlO unimolecular isomerization reaction on the singlet ground state potential energy surface. Electron correlation effects were included via configuration interaction and coupled-cluster methods. Basis sets as complete as triple zeta plus two sets of polarization functions and a set of higher angular momentum functions [TZ(2df,2pd)] were employed. The classical barrier for hydrogen migration from X˜ HAlO to X˜ AlOH is predicted to be 38.4 kcal mol−1 using the TZ(2df,2pd) basis set with the coupled-cluster method including all single and double excitations with the effect of connected triple excitations included perturbatively [CCSD(T)]. After correction for zero-point vibrational energies (ZPVEs), an activation energy of 36.6 kcal mol−1 is obtained. The ΔE for isomerization is −42.2 (−40.5 with ZPVE correction) kcal mol−1 at the same level of theory. The dipole moments of HAlO and AlOH in their equilibrium geometries are 4.525 and 1.040 Debye, respectively, at the same level of theory. A comparison is also made between a theoretically predicted harmonic vibrational frequency and a recently determined experimental fundamental frequency for X˜ AlOH.
    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 94 (1991), S. 5143-5161 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new model of reorientational dynamics in nematic liquid crystals, based on a linear generalized Langevin equation (GLE) representation of the dynamics of a probe molecule, is developed. Derived in the limit of high order, the linearized angular motion of a probe molecule under the influence of director fluctuations is analyzed when the time scale of rotational relaxation is comparable to that of the cooperative modes of the liquid crystal solvent. This model allows negative total solvent contributions (director fluctuations plus a negative cross term) to the spectral density J1(ω) relative to the rotational diffusion contribution, a result predicted experimentally by least-squares data fits. This result cannot be justified in terms of existing theories that assume a separation of time scales between the probe molecule motion and relaxation of the cooperative modes of the solvent. Results from the GLE-based model (and the standard model) are compared to measured spectral densities of a highly ordered spin probe dissolved in a nematic liquid crystal [W. H. Dickerson, R. R. Vold, and R. L. Vold, J. Phys. Chem. 87, 166 (1983)]. Because the frequencies involved are low, the model predictions are very similar and excellent numerical agreement is found with both models. However, because the total solvent contribution is observed to involve inhibition of relaxation relative to the rotational diffusion, the standard model must be rejected on the basis of being physically unreasonable. The GLE model, on the other hand, is on firm physical ground and completely reasonable. The observed negative total solvent contribution to the spectral density can be explained in terms of a coupling of cooperative solvent modes with the molecular reorientation of the probe molecule that interferes with relaxation.
    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 92 (1990), S. 2203-2207 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution electron yield spectra of core electron excitations in condensed Ru3(CO)12 exhibit a pronounced shoulder in the C 1s→π* excitation, due to transitions into unoccupied π levels consisting of linear combinations of the 2π orbitals of the various CO molecular ligands. The O edge near edge spectrum shows a clear and pronounced σ shape resonance transition, about 2 eV lower in energy than in free CO. We develop an intuitive model, which correlates the differences in the relaxation energies associated with the various core electron excitations with changes in the metal to ligand charge transfer process. The consequences of these differences in the core hole screening process with respect to standard models relating the position of the σ shape resonance to the bond length are discussed also.
    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 90 (1989), S. 3537-3558 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Molecular dynamics (MD) simulations of the model SN2 reaction Cl−+CH3Cl→ClCH3+Cl− in water, and variants thereof, are presented. The resulting transmission coefficients κ, that measure the deviations of the rates from the transition state theory (TST) rate predictions due to solvent-induced recrossings, are used to assess the validity of the generalized Langevin equation (GLE)-based Grote–Hynes (GH) theory. The GH predictions are found to agree with the MD results to within the error bars of the calculations for each of the 12 cases examined. This agreement extends from the nonadiabatic regime, where solvent molecule motions are unimportant and κ is determined by static solvent configurations at the transition state, into the polarization caging regime, where solvent motion is critical in determining κ. In contrast, the Kramers theory predictions for κ fall well below the simulation results. The friction kernel in the GLE used to evaluate the GH κ values is determined, from MD simulation, by a fixed-particle time correlation function of the force at the transition state. When this is expressed as a (Fourier) friction spectrum in frequency, marked similarities to the pure solvent spectrum are observed, and are used to identify the water solvent motions that determine the transmission coefficient κ. The deviations of κ from unity, the TST value, are dominated by solvent motions (translational and reorientational) which on the time scale of the recrossings are essentially static configurations. The deviations from the frozen solvent, nonadiabatic limit values κNA are dominated by the hinderd rotations (librations). Finally, the underlying assumptions of the GLE and the GH theory are discussed within the context of the simulation results.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 92 (2002), S. 1643-1648 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Time-resolved electron diffraction harbors great promise for resolving the fastest chemical processes with atomic level detail. The main obstacles to achieving this real-time view of a chemical reaction are associated with delivering short electron pulses with sufficient electron density to the sample. In this article, the propagation dynamics of femtosecond electron packets in the drift region of a photoelectron gun are investigated with an N-body numerical simulation and mean-field model. It is found that space-charge effects can broaden the electron pulse to many times its original length and generate many eV of kinetic energy bandwidth in only a few nanoseconds. There is excellent agreement between the N-body simulation and the mean-field model for both space-charge induced temporal and kinetic energy distribution broadening. The numerical simulation also shows that the redistribution of electrons inside the packet results in changes to the pulse envelope and the development of a spatially linear axial velocity distribution. These results are important for (or have the potential to impact on) the interpretation of time-resolved electron diffraction experiments and can be used in the design of photoelectron guns and streak tubes with temporal resolution of several hundred femtoseconds. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 61 (1990), S. 2439-2448 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: The spatial resolution of a SQUID magnetometer is known to be determined by the size of the magnetometer pickup coil and the distance of this coil from the source of the magnetic field. With the advent of spatial-filtering techniques for converting magnetic field maps to current density images, it is clear that the quality and spatial resolution of the current image is also affected by the detailed characteristics of the transfer function between the current sources and the pickup coil. We show that the quality of a current image can be improved over that obtained with conventional pickup coils by using a multiturn pickup coil whose interturn spacing is adjusted to provide a source-coil transfer function with specific characteristics. This process is functionally equivalent to apodization techniques applied in optical image processing, in which the aperture function of the telescope is adjusted to improve spatial resolution. In coil design, the process of apodization involves designing a magnetometer coil whose transfer function has its first zero at a relatively large spatial frequency. Using apodization, we can decrease coil size and increase the number of turns without a large increase in coil inductance. Our model calculations demonstrate that apodization allows us to optimize the ability of a coil design to image a current distribution, subject to the constraints of signal-to-noise ratio, spatial resolution, and coil inductance.
    Type of Medium: Electronic Resource
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