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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. 5251-5255 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper reports the results of two related experiments: (A) The state-to-state rotational transition probabilities of N2(a 1Πg) in collisions with rare gas atoms (Ar or He) were measured by the technique of two-step multiphoton ionization. Results show that the selection rule antisymmetric–symmetric is obeyed. The transition probability drops rapidly with increasing ||ΔJ||. A propensity rule related to the Π+ or Π− symmetry conservation of the electronic wave function during the collision induced rotational transition holds. (B) The cross section for the rovibronic energy transfer between N2(1Πg) and N2(X 1Σ+g) is found to be ∼28 A(ring)2. N2(a 1Πg) product populations show a Boltzmann-like distribution with a rotational temperature suggesting an equipartition of the available energy among the rotational and translational degrees of freedom of the products. A mechanism invoking an intermediate collision complex along with intermolecular electron exchange may explain the results.
    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 87 (1987), S. 2742-2749 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The collision-induced electronic energy transfer N2(a 1πg,v′) +CO(X 1Σ+,v″=0) →N2(X 1Σ+g,v″) +CO(A 1πg,v′)+ΔE is studied in a gas cell. N2(a 1πg,v′, J′) is prepared by two-photon (2hν1) absorption from the ground state. CO(A 1πg,v′, J′) is probed by two-photon (hν1+hν2) ionization via CO(B 1Σ+) as the resonant intermediate state. Experiments show that the overall energy transfer cross sections exceed that of gas kinetic collisions by a factor of 3–4. The energy mismatch ΔE is the determining factor controlling the branching ratio from one N2(1πg,v′) donor to different vibrational levels of CO(A 1π,v′). For small values of ΔE, CO(A 1πg,v′, J′) shows a Boltzmann-like rotational level population. Its rotational temperature scales with ΔE. About 28% of the excess energy funnels into the rotation of CO(A 1π). An explanation for the observed rotational distribution of CO* and the energy transfer mechanism is given. The rate constants are analyzed in terms of the surprisal.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Photochemistry 17 (1981), S. 249-255 
    ISSN: 0047-2670
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 81 (1981), S. 430-434 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 81 (1981), S. 430-434 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    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 102 (1995), S. 214-225 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This article presents detailed internal and kinetic energy dependent cross sections and reaction rates for the hydrogen atom transfer processes N+2(X 2Σ+g, v+=0–4, J+=2)+H2→N2H++H, which were obtained under single-collision conditions in a guided-ion beam/scattering gas experiment. Preparation of ions in specific states relied on single-color excitation within a resonantly enhanced (2+1) multiphoton ionization scheme. The translational energy of the ions, Elab, was varied from 0.1 eV to approximately 30 eV. A small activation barrier impedes the reaction. Vibronic state preparation of the nitrogen ion is influential on the nature of the energy surface—N+2+H2 or H+2+N2—along which the H atom transfer proceeds. Calculations of model potential energy surfaces suggest that the reaction pathway must involve several exoergic and endoergic channels which open successively as the collision energy increases. A purely collision determined cross section—as would be evidenced by the E−1/2 dependence formulated in the Langevin–Gioumousis–Stevenson model—is observed only within a narrow window of kinetic energies. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 60 (1989), S. 713-716 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A piezoelectric valve is described which delivers intense gas pulses limited by the nozzle for diameters of up to 1.0 mm. Minimum pulse lengths between 0.15 and 0.25 ms (fwhm) are obtained at full opening, depending on the nozzle size. The upper limit of the repetition rate is near 1 kHz. The valve and its modifications meet almost all experimental requirements. In particular, ways of operating in a wide temperature range are outlined. Reliable operation with a remote nozzle at 77 K was recently demonstrated. Nozzle temperatures of more than 1000 K should be possible with a similar setup.
    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 95 (1991), S. 7823-7827 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoelectron spectra are reported from resonantly enhanced multiphoton ionization of N2 via the a 1Πg(v=10–14) states. Ionization from these levels is found to follow a (2+1) pathway resulting in N+2 X 2Σ+g(v+=0–4) ions. The observed branching ratios in the photoelectron spectra reveal a strong propensity for forming ground state ions in a single vibrational state. The results are explained qualitatively by favorable Franck–Condon overlap in the ionizing X 2Σ+g–a 1Πg transition.
    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 108 (1998), S. 527-533 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The widely accepted model descriptions of ion–molecule reactions suggest identical rate constants for the title reaction and the analogous, isoelectronic system N2++H2, which has been the topic of a previous publication from this laboratory. A comparison of both data sets, however, reveals substantial disagreement which we attribute to the absence of energetic resonances between the reagents which characterized the N2+/H2 system. Resonantly enhanced photoionization was exploited to accomplish the state-specific preparation of CO+ (X 2Σ+, v+=0,1). A monoenergetic beam of vibrationally selected ions, tuned within the range 0.01 eV≤Ecm≤10 eV, transits a scattering chamber which confines the neutral, H2. The title reaction was the only channel observed—no evidence of charge transfer or dissociative ionization could be detected. The hydrogen atom transfer turns out to proceed directly. The reactive cross section fails to show the E−1/2 dependence indicative of collision determined processes. The experimental data are perfectly mimicked by an expanded Langevin model which includes additional attractive potential terms. In contrast to the N2+/H2 case, vibrational excitation does not affect the rate of the reaction. © 1998 American Institute of 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 110 (1999), S. 9426-9434 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The charge-transfer process, which is the subject of this paper, is an important link in the chain of reactive events which occur in the E- and F-regions of the earth's atmosphere. The reaction is suspected to proceed via the formation of a short-lived intermediate complex (N2⋅O2)+. The transient existence of this van der Waals molecule has been inferred from molecular orbital and ab initio arguments. To the present day, however, none of the numerous studies focusing on this system has provided proof of its existence. The positive evidence obtained from this experiment is of an indirect nature, based on measurements of the kinetic energy of the released O2+ as a function of the expendable center-of-mass collision energy. The results point to an indirect reaction (i.e., via an intermediate) in the low energy regime, and a direct process once the center-of-mass energy exceeds the bond energy of the complex. A model description which contracts both pictures matches the complete set of energy-dependent cross section data in a very persuasive manner. A competing reactive channel which has also been given attention results in the formation of NO+. The initiation of this reaction requires a cleavage of the N–N bond, which should be eased by vibrational excitation of the reagent ion. The cross section data, however, turn out to be unaffected by such details of reagent state preparation. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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