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Picosecond Dynamics of Intramolecular Vibrational-Energy Redistribution (IVR) in Jet-Cooled Molecules

Citation

Felker, Peter Mark (1985) Picosecond Dynamics of Intramolecular Vibrational-Energy Redistribution (IVR) in Jet-Cooled Molecules. Dissertation (Ph.D.), California Institute of Technology. https://resolver.caltech.edu/CaltechETD:etd-04072008-152253

Abstract

Theoretical and experimental results concerning the dynamical manifestations of intramolecular vibrational-energy redistribution (IVR) in the temporally resolved fluorescence of jet-cooled molecules are presented. A first concern is with the derivation of the characteristics of the beat-modulated fluorescence decays which arise from multilevel vibrational coupling within a molecule. Relations connecting quantum beat frequencies, phases, and modulation depths to coupling parameters are presented. Likely sources of deviations of experimental results from theoretical predictions are considered. And, the direct link between IVR and time-resolved fluorescence experiments is discussed with emphasis placed on the physical interpretation of vibrational quantum beats and the nature of IVR as a function of vibrational energy in a molecule. Secondly, the results of picosecond time-resolved measurements of IVR on jet-cooled anthracene at different excess energies are reported and analyzed. The nature of IVR as a function of vibrational energy, the relevant timescales for the process, and the details of pertinent vibrational couplings are determined. Thirdly, experimental and theoretical results pertaining to the role of molecular rotations in IVR are presented. Finally, experimental results on jet-cooled t-stilbene are reported and analyzed with the aim of assessing the generality of our theoretical treatment and the anthracene results.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:The Herbert Newby McCoy Award, 1983
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Marcus, Rudolph A.
Thesis Committee:
  • Marcus, Rudolph A. (chair)
  • Zewail, Ahmed H.
  • McKoy, Basil Vincent
  • Anson, Fred C.
Defense Date:4 December 1984
Funders:
Funding AgencyGrant Number
NSFDMR-8105034
NSFCHE-821135
IBMUNSPECIFIED
Record Number:CaltechETD:etd-04072008-152253
Persistent URL:https://resolver.caltech.edu/CaltechETD:etd-04072008-152253
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/1.448246DOIArticle adapted for Chapter 3.
https://doi.org/10.1063/1.448247DOIArticle adapted for Chapter 4.
https://doi.org/10.1063/1.448248DOIAritcle adapted for Chapter 5.
https://doi.org/10.1063/1.448249DOIArticle adapted for Chapter 6.
https://doi.org/10.1021/j150669a011DOIArticle adapted for Chapter 7.
https://doi.org/10.1016/0009-2614(83)87375-8DOIArticle adapted for Appendix I.
https://doi.org/10.1103/physrevlett.53.501DOIArticle adapted for Appendix II.
https://doi.org/10.1016/0009-2614(84)85196-9DOIArticle adapted for Appendix III.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:1297
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:08 Apr 2008
Last Modified:02 Dec 2020 01:33

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