CaltechTHESIS
  A Caltech Library Service

The naphthalene sensitized photoracemization of sulfoxides

Citation

Cooke, Robert Sanderson (1970) The naphthalene sensitized photoracemization of sulfoxides. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:04192011-132638953

Abstract

The sensitized photoracemization of alkyl aryl sulfoxides has been shown to result from energy transfer from the singlet state of naphthalene. The possibility of exothermic electronic energy transfer has been ruled out on the basis of spectroscopic data. It is postulated that an exciplex is reversibly formed from an excited singlet state naphthalene molecule and a ground state molecule of the sulfoxide. This excited complex then undergoes radiationless decay converting electronic energy to vibrational energy partitioned between the two components of the exciplex. Enough vibrational energy appears in the aryl sulfinyl center to effect thermal pyramidal inversion with high efficiency. Steric and electronic effects on the rates of fluorescence quenching or of photoracemization are small.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Hammond, George Simms
Thesis Committee:
  • Unknown, Unknown
Defense Date:10 September 1969
Record Number:CaltechTHESIS:04192011-132638953
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:04192011-132638953
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6339
Collection:CaltechTHESIS
Deposited By: Tony Diaz
Deposited On:27 Apr 2011 16:45
Last Modified:26 Dec 2012 04:34

Thesis Files

[img]
Preview
PDF - Final Version
See Usage Policy.

25Mb

Repository Staff Only: item control page