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dc.contributor.authorClarkin, Owen
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date2012-09-11 22:18:20.89en
dc.date.accessioned2012-09-12T13:44:18Z
dc.date.available2012-09-12T13:44:18Z
dc.date.issued2012-09-12
dc.identifier.urihttp://hdl.handle.net/1974/7456
dc.descriptionThesis (Ph.D, Chemistry) -- Queen's University, 2012-09-11 22:18:20.89en
dc.description.abstractIn this work, experimental and theoretical approaches are applied to the study of chemical reaction dynamics. In Chapter 2, two applications of transition state theory are presented: (1) Application of microcanonical transition state theory to determine the rate constant of dissociation of C2F3I after π∗ ← π excitation. It was found that this reaction has a very fast rate constant and thus is a promising system for testing the statistical assumption of molecular reaction dynamics. (2) A general rate constant expression for the reaction of atoms and molecules at surfaces was derived within the statistical framework of flexible transition state theory. In Chapter 4, a computationally efficient TDDFT approach was found to produce useful potential energy surface landscapes for application to non-adiabatic predissociative dynamics of the molecule CS2 after excitation from the ground state to the singlet C-state. In Chapter 5, ultrafast experimental results of excitation of CS2 to the predissociative neutral singlet C-state is presented. The bandwidth of the excitation laser was carefully tuned to span a two-component scattering resonance with each component differently evolving electronically with respect to excited state character during the quasi-bound oscillation. Scalar time-resolved photoelectron spectra (TRPES) and vector time-resolved photoelectron angular distribution (TRPAD) observables were recorded during the predissociation. The TRPES yield of photoelectrons was found to oscillate with a quantum beat pattern for the photoelectrons corresponding to ionization to the vibrationless cation ground state; this beat pattern was obscured for photoelectron energies corresponding to ionization from the vibrationally excited CS2 cation. The TRPAD data was recorded for two general molecular ensemble cases: with and without a pre-excitation alignment laser pulse. It was found that in the case of ensemble alignment (Chapter 6), the “molecular frame” TRPAD (i.e. TRMFPAD) was able to image the purely valence electronic dynamics of the evolving CS2 C-state. The unaligned ensemble TRPAD observable suffers from excessive orientational averaging and was unable to observe the quantum beat. Engineering efforts were also undertaken to eliminate scattered light background signal (Chapter 7, Appendix A) and improve laser stability as a function of ambient pressure (Appendix B) for TRMFPAD experiments.en_US
dc.languageenen
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectFemtosecond Laseren_US
dc.subjectCoincidence Imaging Spectroscopyen_US
dc.subjectScattered Light Background Reductionen_US
dc.subjectDendritic Cupric Oxideen_US
dc.subjectTime Resolved Photoelectron Spectroscopyen_US
dc.subjectEffect of Air Pressure on Laser Performanceen_US
dc.subjectEffect of Weather on Laser Performanceen_US
dc.subjectTransition state theoryen_US
dc.subjectImaging Valence Electronic Dynamicsen_US
dc.subjectNon-Adiabatic Alignmenten_US
dc.subjectTime Resolved Photoelectron Angular Distributionsen_US
dc.subjectExcited Statesen_US
dc.subjectConical Intersectionsen_US
dc.subjectMolecular Frameen_US
dc.subjectPotential Energy Surfacesen_US
dc.subjectTime Dependent Density Functional Theoryen_US
dc.subjectChemical Reaction Dynamicsen_US
dc.subjectFlexible Transition State Theoryen_US
dc.subjectCarbon Disulfideen_US
dc.titleChemical Reaction Dynamics at the Statistical Ensemble and Molecular Frame Limitsen_US
dc.typethesisen_US
dc.description.degreePh.Den
dc.contributor.supervisorWardlaw, Daviden
dc.contributor.supervisorStolow, Alberten
dc.contributor.departmentChemistryen


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