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. doi:10.7907/x48p-n096. 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 Agency	Grant Number
NSF	DMR-8105034
NSF	CHE-821135
IBM	UNSPECIFIED

Record Number:

CaltechETD:etd-04072008-152253

Persistent URL:

https://resolver.caltech.edu/CaltechETD:etd-04072008-152253

DOI:

10.7907/x48p-n096

Related URLs:

URL	URL Type	Description
https://doi.org/10.1063/1.448246	DOI	Article adapted for Chapter 3.
https://doi.org/10.1063/1.448247	DOI	Article adapted for Chapter 4.
https://doi.org/10.1063/1.448248	DOI	Aritcle adapted for Chapter 5.
https://doi.org/10.1063/1.448249	DOI	Article adapted for Chapter 6.
https://doi.org/10.1021/j150669a011	DOI	Article adapted for Chapter 7.
https://doi.org/10.1016/0009-2614(83)87375-8	DOI	Article adapted for Appendix I.
https://doi.org/10.1103/physrevlett.53.501	DOI	Article adapted for Appendix II.
https://doi.org/10.1016/0009-2614(84)85196-9	DOI	Article 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:

16 Apr 2021 23:06

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