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  • American Institute of Physics (AIP)  (2)
  • 2000-2004  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 2568-2577 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Angular distributions of selected rotational states of NO(A 2Σ+,ν=0) products obtained in the 213 nm photodissociation of (NO)2 have been determined in a molecular beam by using the photofragment ion imaging technique. Specifically, images of NO(A,ν=0) products in N=0, 11, and 19 have been recorded, for which the maximum energies available to the NO(X 2Π) products are 2038, 1774, and 1278 cm−1, respectively. The recoil anisotropy parameter of the photofragments, βeff, decreases significantly at low center-of-mass translational energies from its maximum value of 1.36±0.05, and depends strongly on the rotational angular momentum of the photoproducts. This behavior is described well by a classical model that takes into account the transverse recoil component mandated by angular momentum conservation. For each of the observed NO(A) N states, highly rotating NO(X) levels are produced via planar dissociation, and the angular momenta are established at an interfragment separation of about 2.6 Å. For most of the center-of-mass translational energy range, both corotating and counterrotating fragments are produced, but at the lowest energies, only the latter are allowed. The correlated rotational energy distributions exhibit deviations from the behavior predicted by phase space theory, suggesting that exit-channel dynamics beyond the transition state influences the product state distributions. In this study, a new method for image reconstruction is employed, which gives accurate angular distributions throughout the image plane. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 7474-7484 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation of the chloromethyl radical, CH2Cl, to chlorine atom and methylene is examined following excitation at selected wavelengths in the region 312–214 nm. CH2Cl is produced in a molecular beam by using pulsed pyrolysis. Cl and CH2 products are detected by laser ionization and their velocity and angular distributions are determined by using the ion imaging technique. The spectrum obtained by monitoring the Cl fragment yield as function of photolysis wavelength shows that throughout this wavelength region Cl atoms are major products. With 312–247 nm photolysis, the angular distributions are typical of a perpendicular transition (β=−0.7) and the main products are CH2(X˜ 3B1)+Cl(2P3/2). The available energy is partitioned preferentially into the translational degrees of freedom. "Hot band" transitions are prominent in this region even in the molecular beam indicating that the geometries of the ground and excited states of CH2Cl must be very different. With 240–214 nm photolysis, the angular distributions are typical of a parallel transition (β∼1.2), and the predominant products are Cl(2P3/2) and Cl(2P1/2), with CH2(a˜ 1A1) as the main cofragment. A large fraction of the available energy is partitioned into internal energy of CH2(a˜ 1A1). Comparison with the ab initio calculations of Levchenko and Krylov presented in the accompanying paper enables the assignment of the perpendicular and parallel transitions predominantly to 1 2A1←1 2B1 and 2 2B1←1 2B1 excitations, respectively, and both upper states are probably repulsive in the C–Cl coordinate. The electronic states of the products obtained via these two transitions are in agreement with the predictions of a simple diabatic state correlation diagram based on the calculated vertical energies of the upper states. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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