dc.contributor.advisor Weisman, R. Bruce Adams, James Stephen 2009-06-04T00:03:58Z 2009-06-04T00:03:58Z 1989 https://hdl.handle.net/1911/16204 A fundamental question in the chemistry of azoalkanes concerns the nature of their primary bond cleavage: do the two C-N bonds break in a synchronous or a sequential fashion? The photodissociation of an acyclic, unsymmetrical azoalkane, 3-(methylazo)-3-methyl-1-butene (MAMB), was studied using time-resolved coherent anti-Stokes Raman spectroscopy (CARS) to probe for product formation. Appearance kinetics were measured for all three primary photoproducts following excitation. The 3-methyl-1-buten-3-yl radical fragment appeared within 2 ns of excitation, while the methyl radical and N$\sb2$ were formed through decay of a reaction intermediate (the methyldiazenyl radical) having a lifetime of 12 $\pm$ 2 ns. These results directly demonstrate sequential photodissociation. Similar investigations of photodissociation in the bicyclic azoalkane, 2,3-diazabicyclo (2.2.1) hept-2-ene (DBH), were also performed. After excitation to S$\sb1$, DBH dissociated to form N$\sb2$ and a biradical, 1,3-cyclopentadiyl which was observed to decay through ring closure with a lifetime of 235 $\pm$ 50 ns. The nitrogen photoproduct shows an appearance that has a risetime of 20 $\pm$ 5 ns. The nascent vibrational distribution of the nitrogen photoproduct was found to be 82 ($\pm$4)% in v = 0, 13 ($\pm$4)% in v = 1, and 5 (+2/$-$4)% in v = 2, giving a value of 535 cm$\sp{-1}$ for its average vibrational energy content. Observations of the vibration-rotation contour of the precollisional nitrogen revealed a rotational population distribution peaked at low values of J. Such a distribution suggests a transition state in which both C-N bonds are equally stretched and symmetric forces act on the nitrogen centers as the fragments separate. Fluorescence from DBH vapor excited to its S$\sb1$ origin was directly observed to have a rapid dual exponential decay, implying that DBH undergoes an intermediate-case radiationless transition to discrete levels of T$\sb1$ within 5 ns. A photochemical mechanism proposed to explain these findings involves single-step electronic predissociation of DBH from its T$\sb1$ surface to form N$\sb2$ plus triplet 1,3-cyclopentadiyl biradical. By contrast, acyclic azoalkanes are suggested to dissociate through a competing two-step process whose initial step occurs from a twisted T$\sb1$ structure that is not accessible in DBH. 143 p. application/pdf eng Physical chemistry Transient CARS studies of the vapor phase photodissociation of azoalkanes Thesis Text Chemistry Natural Sciences Rice University Doctoral Doctor of Philosophy Adams, James Stephen. "Transient CARS studies of the vapor phase photodissociation of azoalkanes." (1989) Diss., Rice University. https://hdl.handle.net/1911/16204.
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