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  • American Institute of Physics (AIP)  (54)
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  • 1
    Electronic Resource
    Electronic Resource
    Rotational temperature dependence of the branching ratio for the reaction of O+ with HD (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 8120-8123 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate constants and branching fractions for the reaction of O+ with HD have been measured as a function of average center-of-mass kinetic energy (〈KEcm〉) at three temperatures: 93, 300, and 509 K. Both OH+ and OD+ were produced. The rate constants were found to equal 1.2×10−9 cm3 s−1, independent of temperature or 〈KEcm〉. The branching into OH+ was observed to increase with 〈KEcm〉. Differences in the branching fractions were seen at a particular 〈KEcm〉 at different temperatures. These differences are attributed to a rotational temperature dependence such that increasing rotational temperature decreases the fraction of OH+ produced. The data are in agreement with a theoretical calculation and previous measurements.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461291
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  • 2
    Electronic Resource
    Electronic Resource
    The Ar+–He interaction potential and distribution function effects on swarm measurements of Ar++N2 reaction-rate coefficients using helium buffer gas (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 7286-7297 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio potentials for the X 2Σ+1/2, A1 2Π3/2, and A2 2Π1/2 states of ArHe+ are tested as to their ability to describe swarm measurements of gaseous ion transport coefficients. Also tested are potentials based on spectroscopic measurements and model potentials chosen specifically so as to match the transport data. Ar+-ion velocity distributions in a drift tube containing a helium buffer are calculated from the potentials that best match the mobility data, by solution of the Boltzmann kinetic equation. The velocity distributions are used with estimated cross sections for the charge-transfer reaction Ar++N2 to calculate the effects upon the rate coefficients when the distribution differs from a Maxwell–Boltzmann form. The results indicate that the corrections are small at high buffer gas temperatures (293 K and above) and low to moderate electric-field strengths, but become larger at low temperature (82 K) and high fields. The smallness of the corrections confirms that previous rate coefficient measurements in a drift tube show a dependence of the Ar++N2 reaction upon the rotational temperature of N2.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461406
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  • 3
    Electronic Resource
    Electronic Resource
    Rate constant and branching fraction for the reaction of O+(2D,2P) with CO2 (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1483-1484 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate constant and products of the reaction of O+(2D,2P) with CO2 have been measured. The measurements were carried out in a selected ion flow tube by the monitor ion method. The rate constant was found to be 1.06×10−9 cm3 s−1. The reaction was found to proceed by charge transfer (≥95%). This is in contrast to the reaction of the ground O+(4S) state for which the product is O+2. The rate constant for the excited state reaction is the same as that for the ground state reaction and is slightly less than the collisional limiting value.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.459163
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  • 4
    Electronic Resource
    Electronic Resource
    Vibrational quenching of NO+(v) ions in collision with H2, D2, and O2 (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 1648-1651 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibrational quenching rate constants for NO+(v), predominantly in the v=1 state, have been measured at 200 and 293 K in collisions with H2 and D2 and at 200, 293, and 458 K with O2. The rate constants are all very low, corresponding to quenching probabilities ∼10−4. The low rate constants reflect very shallow attractive potential wells. In the case of H2 and D2 this is a consequence of their low polarizabilities. In the case of O2, repulsive chemical interactions offset the electrostatic attraction to yield a shallow attractive well. This is a consequence of the singlet NO+ and triplet ground state O2 not approaching on the attractive NO+3 ground state potential surface, which is a singlet. The temperature dependences of the quenching rate constants are generally slight, indicating that the collision energies are in a range comparable to the attractive well depth and that the quenching is not strongly dominated by either the attractive forces, which would give a negative energy dependence, or by the repulsive forces which would give a positive energy dependence.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456057
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  • 5
    Electronic Resource
    Electronic Resource
    Reactions of Ar+ with halocarbons and of I+ with CF3I (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 173-179 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The gas phase reactions of Ar+ with the halocarbons CF3Cl, CF3Br, CF3I, CF4, C2F6, and C2F4 have been studied using a variable temperature-selected ion flow tube (VT-SIFT) instrument operated at 298 and 500 K. Rate constants and product branching percentages were measured at both temperatures. Ar+ reacts at the collisional rate with all of the above neutrals at both 298 and 500 K. The reactions with CF3X yield CF+3 and CF2X+ for all X (the reaction with CF4 produces only CF+3 ). For X=I, there is an additional channel leading to the ionic product I+. The reaction of Ar+ with C2F6 produces both CF+3 and C2F+5. The reaction of Ar+ with C2F4 forms a rich product spectrum consisting of the ions CF+, CF+2, CF+3, C2F+3, and C2F+4. The reaction product distributions are compared with results from ionization experiments such as photoion–photoelectron coincidence (PIPECO) and electron impact mass spectrometry, and in some cases excellent agreement is found. The reaction of I+ with CF3I, which is a secondary reaction in the Ar+/CF3I system, was investigated at 298 K in separate experiments. This reaction is rapid and forms four product ions: CF+3, CF2I+, CF3I+, and I+2. The results are compared with previously published information.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463605
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  • 6
    Electronic Resource
    Electronic Resource
    Rotational temperature dependence of the branching ratio for the reaction of Kr+(2P3/2) ions with HD (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 7445-7448 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Branching ratios for the reaction of Kr+(2P3/2) with HD, which produces KrH+ and KrD+, have been measured in a variable temperature-selected ion flow drift tube apparatus as a function of average center-of-mass kinetic energy 〈KEcm〉 at two temperatures, 93 and 300 K. At the lowest energy employed, 〈KEcm〉=0.012 eV, the KrD+ channel is favored, and its contribution decreases with increasing kinetic energy. The data are in agreement with previous measurements. The dependence of the branching ratio on the rotational temperature of HD is derived from the data. The rotational temperature dependence is small and appears to be in the opposite direction to the kinetic energy dependence, i.e., increasing rotational energy appears to decrease the fraction of KrH+ produced. The data are compared with models and with the rotational temperature dependence found for the reaction of O+ with HD. Rate constants for the reactions of Kr+(2P3/2) with H2 and HD were measured at 300 K and no drift field and found to be 2.8±0.7×10−10 cm3 s−1 and 4.0±1.0×10−10 cm3 s−1, respectively. The latter number supports the previous beam measurement and disagrees with a previous selected ion flow tube result.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462395
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  • 7
    Electronic Resource
    Electronic Resource
    Branching ratios and rate constants for reactions of 16O− and 18O− with N2O and 14N15N16O (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3448-3452 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Branching ratios for the NO− isotopic products from the gas-phase reactions of 16O− and of 18O− with 14N15N16O have been determined at 143 and 298 K using a variable temperature-selected ion flow drift tube (VT-SIFDT) instrument. The reaction of 16O− yields the products 14N16O− and 15N16O− in approximately equal abundance at both temperatures. The reaction of 18O− produces the four possible NO− isotopes, with the branching ratio being dependent on temperature. For the latter reaction the rate constant for the O− isotope exchange process has been determined at 143 and 298 K. Rate constants for the reaction of O− with N2O (unlabeled reagents) have been measured as a function of ion-neutral average center-of-mass kinetic energy (〈KEc.m.〉) at several temperatures. The temperature dependence of the rate constant is expressed as T−0.5. The energy dependences at different temperatures fall on a single curve and agree well with a previous energy dependence study at 300 K.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457856
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  • 8
    Electronic Resource
    Electronic Resource
    Temperature dependences of rate constants for reactions of CO−4 with NO and SO2 (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5855-5856 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457538
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  • 9
    Electronic Resource
    Electronic Resource
    Rotational temperature dependences of gas phase ion–molecule reactions (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 4848-4852 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A technique for measuring the rotational temperature dependences of gas phase ion–molecule rate constants is presented. The technique involves measuring the kinetic energy dependences of the rate constants at several temperatures in a variable temperature selected ion flow drift tube. For a monatomic ion, comparing the rate constants at the same center of mass kinetic energy at different temperatures yields the dependence of the rate constant on the internal temperature of the reactant neutral. For neutrals in which the vibrational modes are inactive at the temperatures of the experiment, the internal energy dependence is the rotational temperature dependence. Two examples are presented here, one in which rotational energy significantly influences the rate constants, approximately T−0.5, and one in which it does not. Implications for past drift tube experiments are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.455679
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  • 10
    Electronic Resource
    Electronic Resource
    Collisional vibrational quenching of NO+(v) ions (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 4772-4778 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrational quenching rate constants have been measured for NO+(v〉0) ions with 15 neutral quenching molecules by the SIFDT-monitor ion technique. The temperature dependence of the quenching rate constants for the reactions of the neutrals N2, CO2, and CH4 has been investigated from 208 to 450 K. The dependence of the CH4 quenching rate constant on collision energy has been determined in the energy range 0.03–0.12 eV at 208 and 296 K. Also measured are rate constants for some of the reactions pertinent to the monitor ion technique.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454690
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