Transient CARS studies of the vapor phase photodissociation of azoalkanes

dc.contributor.advisorWeisman, R. Bruceen_US
dc.creatorAdams, James Stephenen_US
dc.date.accessioned2009-06-04T00:03:58Zen_US
dc.date.available2009-06-04T00:03:58Zen_US
dc.date.issued1989en_US
dc.description.abstractA 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.en_US
dc.format.extent143 p.en_US
dc.format.mimetypeapplication/pdfen_US
dc.identifier.callnoThesis Chem. 1989 Adamsen_US
dc.identifier.citationAdams, James Stephen. "Transient CARS studies of the vapor phase photodissociation of azoalkanes." (1989) Diss., Rice University. <a href="https://hdl.handle.net/1911/16204">https://hdl.handle.net/1911/16204</a>.en_US
dc.identifier.urihttps://hdl.handle.net/1911/16204en_US
dc.language.isoengen_US
dc.rightsCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.en_US
dc.subjectPhysical chemistryen_US
dc.titleTransient CARS studies of the vapor phase photodissociation of azoalkanesen_US
dc.typeThesisen_US
dc.type.materialTexten_US
thesis.degree.departmentChemistryen_US
thesis.degree.disciplineNatural Sciencesen_US
thesis.degree.grantorRice Universityen_US
thesis.degree.levelDoctoralen_US
thesis.degree.nameDoctor of Philosophyen_US
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