rdf-syntax-grammar
mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Non-eyring temperature dependence of dynamic isotope effects
  name:
    name part: Ruiz, N. Rebecca.
    role:
      role term: creator
  name:
    name part: Singleton, Daniel A.
    role:
      role term: thesis advisor.
  type of resource: text
  genre: bibliography
  origin info:
    place:
      place term: txu
    date issued: 2010
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: electronic
    form: remote
    extent: 1 online resource.
  abstract: Our group has recently described a new form of kinetic isotope effect that arises from dynamic selectivity in the bifurcation of a reaction pathway on the slope of an energy surface. Since the selection between products does not occur at a potential energy saddle point, we proposed that the isotope effect is decided by dynamic factors that are not necessarily related to zero point energy effects on the surface. As an alternative explanation, it has recently been suggested that variational transition state theory can account for these isotope effects. The dynamic explanation and variational transition state theory explanation make distinct predictions as to the temperature dependence of these isotope effects. I describe here my studies of the temperature dependence of the intramolecular isotope effects for the reaction of singlet oxygen with gemtetramethylethylene- d₆. The selectivity observed for this reaction across a broad temperature range is clearly a non-Eyring distribution and thus the mechanism cannot be adequately described solely using transition state theory or even some variation of it. After using these results to evaluate competing theories it was concluded that this mechanism could only be properly understood using a dynamic explanation.
  note: by N. Rebecca Ruiz.
  note: "Major Subject: Chemistry"
  note: Title from author supplied metadata (automated record created 2010-03-12 12:08:51).
  note: Electronic resource.
  note: Master of Science Texas A&M University 2006 http://hdl.handle.net/1969.1/ETD-TAMU-1057
  note: Includes bibliographical references.
  note: Text (Thesis)
  subject:
    topic: Major chemistry
  subject:
    topic: Dynamic
  subject:
    topic: Eyring
  identifier: http://hdl.handle.net/1969.1/ETD-TAMU-1057
  record info:
    record content source: TXA
    record creation date: 100423
    record change date: 20151201120053.0
    record identifier: in00002579934