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  • 1
    Electronic Resource
    Electronic Resource
    Dynamics of vibrationally excited ozone formed by three-body recombination. I. Spectroscopy (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5202-5208 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectrally resolved infrared fluorescence near 10 μm from vibrationally excited O3(ν3) has been observed in a cryogenic reactor facility at low pressure. The excited O3(v) is formed principally by three-body recombination of O and O2 in flowing, microwave-discharged O2/Ar mixtures at 1 Torr and 80 K. The spectral resolution is sufficient to permit identification and assignment of band centers for up to five quanta of stretching excitation. The observed transition frequencies are consistent with those predicted from a Darling–Dennison perturbation treatment. The spectra, which sample the recombination/deactivation sequence in its early to middle stages, indicate surprisingly little intermode coupling, being predominantly ν3 in character. There is also evidence of O3(v) excitation by near-resonant V–V coupling between O3 and O2(v=2). The spectroscopic analysis of the data is described, and considerations for scaling the spontaneous transition probabilities with vibrational level are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453688
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  • 2
    Electronic Resource
    Electronic Resource
    Dynamics of vibrationally excited ozone formed by three-body recombination. II. Kinetics and mechanism (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5209-5221 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectrally resolved infrared chemiluminescence from vibrationally excited ozone, O3(v), has been used to study the reaction kinetics of O3(v) in discharged O2/Ar mixtures at ∼1 Torr and 80–150 K. Dependences of the excited state number densities on temperature and O2 mole fraction indicate O3(v) is formed primarily by three-body recombination of O with O2 and is destroyed by rapid chemical reaction with O. Several secondary excitation reactions involving vibrationally and electronically excited O2 are also indicated. The data are treated with a detailed steady-state analysis of the discharge kinetics, to extract estimates for rate coefficients of the key elementary reactions. The effective "quasinascent'' state distribution in recombination is also inferred; this distribution shows selective recombination into the asymmetric stretching mode, but an apparently statistical (i.e., collisionally scrambled) behavior among the vibrational states within that mode. The results are discussed in terms of the detailed dynamics of three-body recombination.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453689
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  • 3
    Electronic Resource
    Electronic Resource
    The stability of N2(A' 5Σ+g) (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 1796-1803 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The energy and stability of the "high spin'' 7Σ and 5Σ states of N2 have been the subject of many theoretical efforts. These states play an important role in N-atom recombination. The collisional coupling of these states to other excited electronic states strongly influences the electronic emission spectrum of N2 observed in atom recombination. Since these states are not dipole coupled to lower excited electronic states of N2 , they are considered metastable and are possible candidates for high energy density storage media. We have examined the stability of N2(5Σ) state in a discharge flow reactor. The 5Σ state is produced from the N2(A 3Σ) energy pooling reaction and probed via laser-induced fluorescence on the C‘ 5Π–A' 5Σ transition. While no laser-induced fluorescence from excitation of the A' state is observed, comparison of signal levels with laser-induced fluorescence on the B 3Πg–A 3Σ−u transition enables us to establish an upper limit on the gas phase lifetime of this state at pressures of a few Torr. Experimental evidence is presented which suggests that the primary mode of A'-state quenching is through collisional coupling to the B 3Πg state. However, other matrix isolation experiments suggest that the A' state may be stabilized in cryogenic rare gas matrices.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458061
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  • 4
    Electronic Resource
    Electronic Resource
    The excitation of IF(B 3Π0+) by N2(A 3Σ+u) (1985)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 5602-5609 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Experiments in a discharge-flow reactor show that the energy-transfer reaction between N2(A 3Σ+u ) and IF(X 1Σ+) is extremely rapid (ktotal=2.0×10−10 cm3 molecule−1 s−1) with 40% of the quenching collisions resulting in fluorescence from IF(B 3Π0+).The reaction populates IF(B) vibrational levels up through v'=9 and produces v'=0–6 with about equal probability at low pressure. The vibrational distribution relaxes rapidly in collisions with the reactor bath gas even at pressures of a few Torr. The vibrational relaxation rate coefficients for levels 3–6 of IF(B) in a mixture of 80% Ar/20% N2 are about 3×10−12 cm3 molecule−1 s−1, with levels 1 and 2 being a little slower. Differences in IF excitation between N2(A) v'=1 and v'=0 are small (kv'=1/kv'=0≤1.2). Electronic quenching of the IF(B) is sufficiently slow that even at higher reactor pressures radiative decay is the dominant loss. Rate coefficients for quenching N2(A), by CF3I, and NF3 and for vibrational relaxation of N2(A,v'=1) by CF4, CF3H, CH4, and SF6 also are reported.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.449684
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  • 5
    Electronic Resource
    Electronic Resource
    Infrared spectra (2–16 μm) of ArI Rydberg emission from a microwave discharge plasma (1985)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 82 (1985), S. 681-692 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared (2–16 μm) emission from Ar Rydberg atoms, excited in a conventional low-pressure microwave discharge plasma, has been observed in the cryogenic COCHISE reactor/spectrometer facility. The observed spectrum is very complex but is identifiable using the detailed energy level structure and optical selection rules for ArI. Detailed transition probabilities for dipole-allowed transitions between 2 and 16 μm were computed using the Coulomb approximation. Comparisons of observed and predicted spectra show that substantial long wavelength infrared (LWIR) emission (∼12 μm) arises from Rydberg states near the ionization limit; these states must have kinetically enhanced populations in order to account for the observed emission intensities. The results are interpreted in terms of a radiative/collisional cascade sequence initiated by dissociative recombination of Ar+2 with energetic electrons in the active discharge.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.448545
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  • 6
    Electronic Resource
    Electronic Resource
    Branching ratios for infrared vibrational emission from NO(X 2Π,v'=2–13) (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 7555-7563 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ratios of overtone and fundamental vibrational Einstein coefficients for NO(X 2Π) have been measured by spectrally resolved infrared chemiluminescence near 2.7–3.3 μm and 5.2–6.8 μm. The reactions of N(2D,2P) with O2, in the presence of a small background of He in a cryogenic low-pressure reactor, generated vibrationally excited, rotationally cold (60 K) NO(v), whose emission spectra were recorded with high spectral resolution. Least-squares spectral fitting analysis of the observed overtone and fundamental spectra gave vibrational band intensities, whose ratios at each emitting vibrational level v' yielded the (Δv=2)/(Δv=1) Einstein coefficient ratios for v'=2–13. The results provide comparisons to previous theoretical and experimental data, and reflect the behavior of the dipole moment function for NO(X 2Π). The measured ratios indicate an overtone Einstein coefficient A2,0=0.94±0.11 s−1 for an assumed fundamental value A1,0=13.4 s−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462407
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  • 7
    Electronic Resource
    Electronic Resource
    The dipole moment and infrared transition strengths of nitric oxide (1998)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 3409-3417 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The electric dipole moment function for NO(X 2Π) is determined by nonlinear least-squares analysis of experimental data, including previously reported (Δv=2)/(Δv=1) transition branching ratios for v′≤13. Polynomial fits to the dipole moment function are determined over the range of internuclear separation from 0.97 to 1.50 Å. The fitted dipole moment functions agree well with previous ab initio predictions, but differ somewhat at the larger internuclear separations. The observed dipole moment functions are used to compute rotationless Einstein coefficients for Δv=1–4 vibrational transitions with v′≤20. The absolute Δv=1 and Δv=2 Einstein coefficients are well determined by this analysis, especially for v′≤12. The results provide a firm basis for determinations of vibration-rotation emission intensities of NO(X 2Π) in high-temperature or nonequilibrium chemiexcitation systems. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.476936
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  • 8
    Electronic Resource
    Electronic Resource
    Rovibrational excitation of nitric oxide in the reaction of oxygen with metastable atomic nitrogen (1989)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 93 (1989), S. 1097-1107 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100340a016
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  • 9
    Electronic Resource
    Electronic Resource
    Rate constant for carbon monoxide + molecular oxygen = carbon dioxide + atomic oxygen from 1500 to 2500.deg. K. Reevaluation of induction times in the shock-initiated combustion of hydrogen-oxygen-carbon monoxide-argon mixtures (1974)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 78 (1974), S. 497-500 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100598a007
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