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  • 1
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 67 (1996), S. 2257-2268 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A new photoelectron spectrometer has recently been used to analyze the energy and spatial distribution of photoelectrons produced by multiphoton ionization of rare gases. It is based on the analysis of the image obtained by projecting the expanding electron cloud resulting from the ionization process onto a two-dimensional position sensitive detector by means of a static electric field. In this article, we present the principle of this imaging spectrometer and the relevant equations of motion of the charged particle in this device, together with an inversion method that allows us to obtain the energy and angular distribution of the electrons. We present here the inversion procedure relevant to the case where the electrostatic energy acquired in the static field is large as compared to the initial kinetic energy of the charged particles. A more general procedure relevant to any regime will be described in a following article. © 1996 American Institute of 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 98 (1993), S. 5419-5430 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Coupled channel calculations of thermal collisions of Xe(5p5nl) (nl=6s,6p,5d) with He and Ar have been performed using potential curves and coupling matrix elements that we previously calculated. Coupling among all of the closely spaced 6s', 6p, and 5d fine structure levels of Xe is fully included. These excited levels lie in the range 76 000–84 000 cm−1 above the Xe ground state, and the spacing of adjacent levels ranges from 84 to 1460 cm−1. Rate constants for level-to-level transitions are calculated at T=300 and T=800 and compared with recent experiments; agreement is generally good. The rate constants are very sensitive to the specific initial and final levels and to the collision partner. This sensitivity can be explained by the pattern of crossings and avoided crossings of potential curves corresponding to individual fine structure levels. The calculations thereby illustrate the importance of spin–orbit effects in heavy atom systems and provide insight into a large amount of data.
    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 96 (1992), S. 2099-2113 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Interatomic potentials for the interaction of low-lying excited states of Xe(5p5nl) (nl=6s,6p,5d) with He and Ar have been calculated. A novel method has been developed that refines and extends the results of ab initio electronic structure calculations by incorporating available spectroscopic information using a model Hamiltonian. The ab initio calculations treat the heavy-atom cores using relativistic effective potentials and include spin–orbit effects at the configuration-interaction level. The model Hamiltonian depends on a small number of physically sensible parameters, some of which are extracted from the ab initio calculations, and others of which are determined more accurately from spectroscopy. The model Hamiltonian is then used to recalculate the potential curves and coupling matrix elements. The results obtained have significant implications for two classes of recent experiments. Recent measurements of rate constants for state-to-state transitions of Xe* induced by collisions with He or Ar have revealed that the magnitude of the rate depends strongly on the specific transition and collision partner. The present adiabatic potential curves exhibit several regions of strong coupling, which can be associated with the crossings of "diabatic states,'' and which can be correlated with those transition rates found to be large. Other experiments have measured multiphoton ionization spectra of XeAr, thereby providing information on the vibrational levels of the excited-state potentials that can be compared with the present calculations.
    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 90 (1989), S. 5299-5308 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A two-step photoionization scheme is used to determine vibrational frequencies of the n=3 Rydberg states of triatomic hydrogen. Symmetric-stretch frequencies in orthotrihydrogen of 3212.1 and 3168 cm−1 are measured for the N=1 levels of the states 3s 2A'1 and 3d 2E‘, respectively. Transitions to bending-mode excited levels in the 3d states and overtone levels of the 3p 2 E' state are observed also.
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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. 3944-3954 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The previous study [G. E. Gadd and T. G. Slanger, J. Chem. Phys. 92, 2194 (1990)] of the v=0–6 levels of the NO(B 2Π) valence state has been extended to the v=7 level, which is of particular interest because it lies at the first dissociation limit of the molecule, and also in a region where strong homogeneous mixing with the C 2Π Rydberg state manifests itself. Thus, the v=7 radiative lifetime can be affected by both these interactions, which are dependent on rotational level. It has often been argued that the B 2Π3/2 spin–orbit component interacts strongly with C 2Π1/2,3/2, whereas the B 2Π1/2 component is unperturbed. We show here that "unperturbed'' is a relative term and that a sensitive way to demonstrate that even the B 2Π1/2 levels are mixed with the C 2Π state is to measure the intensity branching in the B–X 7–v‘ vibrational progression from fluorescent spectra, for different rotational levels. In the present study, excitation of these levels is carried out on the B–X 7–0 band at 191–192 nm. We have investigated the lifetimes of both spin–orbit components of B 2Π(v=7) and find that the decreasing interaction with the C 2Π state with increasing rotational level, in spite of the increasing energy above the dissociation limit, leads to a steady increase in radiative lifetime. The value reached at high J is 350–400 ns, whereas the lifetimes of the Ω=1/2 levels that lie below the dissociation limit approach a value of 600–700 ns, consistent with the extrapolation of lifetime data for v=0–6.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 2219-2228 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A double-resonance technique is employed to measure the positions of energy levels of the second 3Πg state of H2. Vibrational levels of this state with v〉3 lie above the ionization threshold of H+2, and are observed both to autoionize and dissociate. This state, 23Πg, arises from the homogeneous interaction between the singly excited 1sσg3dπg and 1sσg4dπg diabatic Rydberg states with the core-excited 2pσu2pπu state. The energy-level spacings are in good agreement with a simple model calculation for the interacting potentials. We also include a listing of autoionizing levels lying in the same energy range.
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  • 7
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 92 (1988), S. 4094-4099 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 105 (1996), S. 9393-9402 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The technique of cavity ring-down (CRD) spectroscopy is particularly useful for measuring absorptions of very weak optical transitions. We have in this manner investigated the 40 950–41 300 cm−1 region in O2, where only absorption in the O2(A 3Σ+u–X 3Σ−g) 11-0 band had been previously identified. Five new bands have been discovered in this range—the A′ 3Δu–X 3Σ−g 12-0 and 13-0 bands, the c 1Σ−u–X 3Σ−g 17-0 and 18-0 bands, and the A 3Σ+u−X 3Σ−g 12-0 band. The origins of the F1 and F2 components of the latter lie only 7 cm−1 below the lowest dissociation limit, and 15 lines have been identified. No F3 levels were observed; apparently all are above the dissociation limit. The high instrumental sensitivity of the CRD technique has allowed observation of weak lines of the A–X 11-0 band, and 12 of the 13 branches have been identified and their intensities measured. A very low upper limit has been set on the intensity of the thirteenth branch, Q13. We find 107 unidentified lines in the region, the stronger ones (19) lying in the vicinity of lines of the A–X 11-0 band. The weaker ones (88) are spread throughout the spectral region, up to and even beyond the O2 dissociation limit, and probably have their origin in transitions to very weakly bound O2 states, which may have atmospheric significance. These weaker lines have intensities that are typically 1%–5% of the strong A–X 11-0 band lines. © 1996 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 90 (1986), S. 6842-6848 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 113 (2000), S. 8514-8520 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Numerous atomic lines appearing in the terrestrial nightglow can be measured by HIRES, the echelle spectrometer on the 10 meter Keck I telescope on Mauna Kea. The observable nightglow lines include emissions from Na, K, Hg, Ne, N, O, and H. Agreement between the line positions and those from National Institute of Science and Technology (NIST) compilations is excellent for well-known lines, typically 2 mÅ or better. For lines which are not well-known, or cannot be measured directly in the laboratory, deviations are significant. In particular, for the optically forbidden N(2D–4S) transition the differences are substantial, 20 and 24 mÅ for the two components. Apart from improving the line positions for this transition, we also correct an error that has been perpetuated in the aeronomic literature for the last 30 years concerning the transition wavelengths. The potassium D1 line, recently discovered in the HIRES sky spectra, exhibits a position difference of 11 mÅ between the NIST and HIRES values, significant for astronomical applications. The HIRES value is shown to be in close agreement with the latest laboratory study. For the Balmer series of H lines, we report the first ground-based observation of Hγ in the geocorona, and we confirm that the positions of the H(α,β,γ) lines agree with the expectation that the principal source is direct solar resonance excitation, with a 5%–6% cascading contribution in the case of Hα. The absolute average intensities of the three lines are 3600, 900, and ∼210 millirayleighs (mR), respectively. © 2000 American Institute of Physics.
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