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  • Articles  (3)
  • American Institute of Physics (AIP)  (3)
  • 1995-1999  (3)
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  • 1999  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 6413-6421 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Accurate spin–orbit splitting constants (Av+) for the vibrational levels v+=0–41 of CO+(A 2Π3/2,1/2) have been determined in a rotationally resolved pulsed field ionization photoelectron study. A change in slope is observed in the v+ dependence for Av+ at v+(approximate)19–20. This observation is attributed to perturbation of the CO+(A 2Π) potential by the CO+(B 2Σ+) state. Theoretical Av+ values for CO+(A 2Π3/2,1/2, v+=0–41) have also been obtained using a newly developed ab initio computational routine for spin–orbit coupling calculations. The theoretical Av+ predictions computed using this routine are found to be in agreement with the experimental Av+ values for CO+(A 2Π3/2,1/2, v+=0–41). Similar Av+ calculations obtained for O2+(X 2Π3/2,1/2g, v+=0–38) are also in accord with the recent experimental Av+ values reported by Song et al. [J. Chem. Phys. 111, 1905 (1999)]. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reaction between ground state carbon atoms, C(3Pj), and hydrogen sulfide, H2S(X1A1), was studied at four average collision energies between 16.7 and 42.8 kJ mol−1 using the crossed molecular beam technique. The reaction dynamics were deducted from time-of-flight spectra and from laboratory angular distributions combined with ab initio calculations. These data suggest that the reaction proceeds through an addition of C(3Pj) to the sulfur atom to form a triplet CSH2 van der Waals complex. Successive H atom migration on the triplet or singlet surface forms a thiohydroxycarbene intermediate, HCSH, which decomposes through a tight exit transition state to HCS(X2A′)+H(2S1/2). At lower collision energies, a weak L-L′ coupling leads to isotropic center-of-mass angular distributions. As the collision energy rises, the angular distributions show increasing forward scattering thereby documenting that the reaction goes through an osculating HCSH complex. Identification of the HCS isomer under single collision conditions is a potential one-step pathway by which to form organo-sulfur molecules in interstellar environments during the collision of the comet Shoemaker-Levy 9 with Jupiter, and in combustion flames of sulfur containing fuels. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 6154-6157 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Model chemistries that employ additivity schemes have become increasingly popular within the chemical community. These approaches are predicated upon the assumption that less rigorous (and, therefore, less expensive) calculations may be combined to approximate a more accurate (and otherwise intractable) level of theory. Most of these models make some use of an empirical correction, the desirability of which is at best questionable. The present paper critically examines the importance of one such correction (the "higher-level correction") to the most widely used additivity method (the Gaussian model). An alternative approach, which does not depend upon any sort of ad hoc empiricism, is also outlined. The current model is found to offer accuracy comparable to that of the Gaussian model. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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