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  • 1
    Electronic Resource
    Electronic Resource
    Negative ion chemistry of SF4 (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 8865-8873 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A selected ion flow tube was used to conduct an extensive study of negative ion–molecule reactions of SF4 and SF−4. Rate constants and product ion branching fractions were measured for 56 reactions. The reactions bracket both the electron affinity of SF4 (1.5±0.2 eV or 34.6±4.6 kcal mol−1) and the fluoride affinity of SF3 (1.84±0.16 eV or 42.4±3.2 kcal mol−1). These results may be combined to give the neutral bond energy D(SF3–F)=3.74±0.34 eV or 86.2±7.8 kcal mol−1, independent of other thermochemical data except for the accurately known electron affinity of F. The heat of formation of SF−4 is derived from the electron affinity of SF4: ΔfH(SF−4)=−9.2±0.3 eV or −212.9±7.5 kcal mol−1. Lower limits to EA(SF2) and EA(SF3) are deduced from observation of SF−2(35%) and SF−3(65%) ion products of the reaction S−+SF4. Rapid fluoride transfer from both SF−2 and SF−3 to SF4 places upper limits on the electron affinities of SF2 and SF3. The combined results are 0.2 eV≤EA(SF2)≤1.6 eV and 2.0 eV≤EA(SF3)≤3.0 eV. We review the status of measurements of EA(SFn), n=1–7. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468940
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  • 2
    Electronic Resource
    Electronic Resource
    Negative ion reactions with PF5 and the electron affinity of PF5 (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 7200-7205 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate coefficients and product branching fractions have been determined for 31 ion–molecule reactions involving PF5 or PF−5. About half of the reactions studied show an ion–molecule association channel. NH−2 and OH− reaction with PF5 yields HF product. F− and electron transfer channels are also observed in many of the reactions studied. Consideration of the efficiency of the electron transfer channel in these reactions leads to the conclusion that the adiabatic electron affinity of PF5 is 0.75±0.15 eV.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.466918
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  • 3
    Electronic Resource
    Electronic Resource
    Dynamics of linear and T-shaped Ar–I2 dissociation upon B←X optical excitation: A dispersed fluorescence study of the linear isomer (1999)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 7844-7856 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the dispersed fluorescence spectra of the linear and the previously well-studied T-shaped isomers of Ar–I2 following B←X optical excitation for vpump=16–26, below the I2 dissociation limit. The linear isomer has a continuum excitation spectrum. For excitation at the highest pumping energy (vpump=26), the product vibrational state distribution is nearly identical to that observed for excitation above the I2(B) dissociation limit; it shows a broad, nearly Gaussian distribution of I2(B) vibrational states, with about 22% of the available excess energy deposited in translation of the Ar+I2. This gives direct evidence that the "one-atom cage" effect seen above the I2(B) dissociation limit is attributable to the linear Ar–I2 isomer. The product vibrational state distribution becomes increasingly Poisson for decreasing excitation energies, and only about 7% of the excess energy is deposited in translation for vpump=16. The bond energy in the linear isomer is determined from the spectra, 170(±1.5)≤D0″(linear Ar–I2(X))≤174(±1.5) cm−1. A bond energy of D0″(T-shaped Ar–I2(X))=142±15 cm−1 is estimated based on the linear to T-shaped population ratio observed in the beam, which is about 90 cm−1 smaller than that determined from fluorescence spectra. We suggest that electronic quenching in the T-shaped isomer is nearly 100% for the highest vibrational level produced by vibrational predissociation. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.480120
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  • 4
    Electronic Resource
    Electronic Resource
    Reactivity of the radical anion OCC- (1993)
    s.l. : American Chemical Society
    Journal of the American Chemical Society 115 (1993), S. 7407-7414 
    Details
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ja00069a045
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  • 5
    Electronic Resource
    Electronic Resource
    Laser photoelectron spectroscopy of CrH−, CoH−, and NiH−: Periodic trends in the electronic structure of the transition-metal hydrides (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 1549-1556 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The laser photoelectron spectra of CrH−, CoH−, and NiH− and the analogous deuterides are reported. The spectra are interpreted using a qualitative description of the electronic structure for the hydrides. This model is used to assign off-diagonal transitions in the photodetachment to low-spin states of the neutrals, and diagonal transitions to high-spin states of the neutrals. These data are used to identify the high-spin states of CoH and NiH; several other states of CrH, CoH, and NiH are also identified. Periodic trends in the bond lengths, vibrational frequencies, and electronic excitation energies for the MnH through NiH molecules are examined. Electron affinities are reported for CrH (0.563±0.010 eV), CoH (0.671±0.010 eV), and NiH (0.481±0.007 eV), and the corresponding deuterides.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453214
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