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  • 11
    Electronic Resource
    Electronic Resource
    Flowing afterglow apparatus for the study of ion–molecule reactions at high temperatures (1996)
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 67 (1996), S. 2142-2148 
    Details
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: We describe two versions of a high temperature flowing afterglow apparatus. With a stainless steel flow tube wrapped with heating tape we have obtained data over the range 300–1300 K. In a version with a ceramic flow tube in a commercial furnace we have obtained data over the range 300–1600 K. The ceramic version is designed to take data up to 1800 K, but we have encountered experimental problems at the upper temperature range. The design modifications to a standard flowing afterglow needed to make measurements at elevated temperatures are described in detail, as are problems associated with operating at elevated temperatures. Samples of data are given. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1147028
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  • 12
    Electronic Resource
    Electronic Resource
    A reexamination of the vibrational–vibrational energy transfer from N2(v) to NO+ (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 6579-6582 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have reexamined whether N2(v=1) transfers its vibrational quantum to NO+(v=0). In light of recent results that show that CH3I does not charge transfer rapidly with NO+(v=1), we show that previous measurements could not have detected vibrational–vibrational (V–V) energy transfer from N2(v=1) to NO+(v=0). We have made measurements to examine this process by using C2H5I as the monitor for NO+(v=1). Our results show that NO+(v(approximately-greater-than)0) is indeed produced from reaction of NO+(v=0) with N2(v) but these results cannot be used to distinguish between resonant V–V energy transfer from N2(v=1) to NO+(v=0) and V–V, T energy transfer from higher levels of N2(v).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465849
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  • 13
    Electronic Resource
    Electronic Resource
    Erratum: The photodissociation spectrum of SO2+ [J. Chem. Phys. 84, 1215 (1986)] (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3582-3582 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465113
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  • 14
    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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  • 15
    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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  • 16
    Electronic Resource
    Electronic Resource
    Evidence for an influence of rotational energy on the rate constants for the reaction of Ar+(2P3/2) with N2 (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4761-4765 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate constants for the charge transfer reaction of Ar+(2P3/2) with N2 were measured as a function of average center-of-mass kinetic energy (〈KEcm〉) at three temperatures. The rate constants increase rapidly with (〈KEcm〉) at all temperatures. The thermal activation energy is derived to be 0.07 eV, which is approximately the value of the endothermicity of the reaction when N+2 (v=1) is produced. The rate constants vary with temperature at a particular 〈KEcm〉, indicating either an effect due to differing energy distributions in the drift tube at different temperatures or that the reactivity depends on the rotational temperature of N2. Comparing the data at constant average total energy indicates that translational and rotational energy have a similar effect on the reactivity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458666
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  • 17
    Electronic Resource
    Electronic Resource
    Kinetic energy, temperature, and derived rotational temperature dependences for the reactions of Kr+(2P3/2) and Ar+ with HCl (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1149-1157 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate constants for the reactions of Kr+(2P3/2) with HCl and DCl and of Ar+ with HCl have been measured as a function of reactant ion/reactant neutral average center-of-mass kinetic energy (〈KEc.m.〉 ) at several temperatures. The measurements were made using helium as the carrier gas. From these data we have derived the dependences of the rate constants on the rotational temperature of H(D)Cl. Rate constants for the reaction of Kr+(2P1/2) with HCl have also been measured as a function of temperature. The rate constants for all of the reactions were found to decrease with increasing temperature. The rate constants were also found to decrease with increasing 〈KEc.m.〉 at low 〈KEc.m.〉 but then to increase at higher 〈KEc.m.〉 . A significant rotational temperature dependence of the rate constant was derived for the reaction of Kr+(2P3/2) with H(D)Cl. The analogous derivation for Ar+ reacting with HCl showed the rate constant for this reaction to be independent of the rotational temperature of HCl within experimental uncertainty.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.459178
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  • 18
    Electronic Resource
    Electronic Resource
    Rate constants for quenching the A˜ 2A2 state of SO+2 by atmospheric gases (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 5553-5560 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of ion source pressure on the cross sections for photodissociation of SO+2 has been measured systematically at λirr =4735 and 4795 A(ring). Using a Stern–Volmer treatment modified to account for the dependence of source residence time on pressure, rate constants have been measured for quenching the A˜ 2A2 (v1,v2=3,3) and A˜ 2A2(v1,v2=3,0) states of SO+2 by N2O, SO2, CO2, and N2. With SO2 and N2O as quenchers the rate constants range between 1.0 and 6.5 times the theoretical thermal capture rate constants ("Langevin limit''). The occurrence of several resonant and many near-resonant charge transfer processes is proposed to explain the unusually large rate constants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454566
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  • 19
    Electronic Resource
    Electronic Resource
    Temperature, kinetic energy, and internal energy dependences of the rate constant and branching fraction for the reaction of O+ (4S) with CO2 (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 270-274 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate constants and branching fractions were measured for the reaction of O+ (4S) with CO2 as a function of average ion-neutral center-of-mass kinetic energy (〈KEcm〉) at several temperatures. The reaction produces both O+2 and CO+2 as product ions. The total rate constants were found to be nearly collisional at low 〈KEcm〉 and to decrease slightly at higher 〈KEcm〉. No temperature dependence of the rate constants was found at any given 〈KEcm〉, indicating that neither CO2 rotational excitation nor CO2 bending mode excitation has much effect on the overall reactivity. In contrast, the branching fraction for the endothermic charge transfer channel leading to CO+2 was found to increase with increasing 〈KEcm〉 and also to increase with temperature at fixed 〈KEcm〉. Analysis of the data indicates that the branching fraction depends on the total energy in the system (electronic, kinetic, rotational, and vibrational).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462514
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  • 20
    Electronic Resource
    Electronic Resource
    The effect of low frequency vibrations in CH4 on the rate constant for the reaction of O+2 (X 2Πg, v=0) with CH4 (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 275-284 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate constant for the reaction of O+2 with CH4 has been measured as a function of average center-of-mass kinetic energy, 〈KEcm〉, at several temperatures over the range 93–545 K. The rate constant decreases with increasing 〈KEcm〉 at low 〈KEcm〉 and increases at higher 〈KEcm〉; the position of the resulting minimum depends on temperature. We have observed small differences in the rate constants measured at the same total 〈KEcm〉 but at different temperatures in the low temperature regime (T≤300 K). These differences, i.e., decreasing rate constants with increasing temperature, are discussed in terms of the possibility of a rate constant which is dependent upon rotational energy. At higher temperatures, 430 and 545 K, we find that the rate constant is significantly larger than that measured at lower temperatures at a given 〈KEcm〉. This enhanced reactivity is attributed to vibrational excitation in the CH4. From these data, we derive a rate constant for vibrationally excited CH4 (in the low frequency modes) that is approximately a factor of 20 greater than the rate constant for the ground vibrational state. The data disagree with an early study of this type at low temperature. The disagreement is discussed, and arguments are presented which indicate that the earlier data are in error at low temperature with an applied drift field. The use of these data for deriving effective reaction temperatures in other nonthermal experiments is also discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462515
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