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Investigation of coriolis mixing in benzene

Citation

Runnels, John Hulett (1983) Investigation of coriolis mixing in benzene. Master's thesis, California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:03292010-084636927

Abstract

An explanation for some recent observations in the electronic absorption spectrum of benzene by Schlag and coworkers is proposed. Several vibrational lines of the S_0 to S_1 transition have been studied by these authors with the Doppler—free, two—photon technique developed earlier. The resolution of this technique is so high that individual Δ J=0, Δ K=0 rotational lines in the Q—branch of a given vibrational transition may be seen in the electronic absorption spectrum. A major progression in the two—photon spectrum is the 14^1_0 1^n_0 progression. It was found that the 14^1_0 1^0_0 and 14^1_0 1^1_0 transitions had well—resolved rotationalstructure, but the 14^1_0 1^2_0 transition had reduced, not well resolved rotational structure--except for the prominent K=0 lines for small to medium values of J. This suggested to us Coriolis mixing. The model presented here utilizes a suggestion of Riedle et al.The Coriolis coupling to neighboring vibrational states is followed by a rapid radiationless depletion of these states, consistent with the decreased fluorescence yield observed by Wunsch et al. Estimates are made of the density of states of the various symmetries; these estimates are then used to estimate the extent of the relevant Coriolis mixing. The model results in a large decrease in intensity of non—zero K lines relative to the K=0 lines for the 14^1_0 1^2_0 transition, but not for the 14^1_0 1^0_0 and 14^1_0 1^1_0 transitions, in agreement with the experimental observations, making a few assumptions discussed below, but without the use of adjustable parameters. Predictions are then made for the rotational structure of other strong transitions in the two—photon spectrum of benzene.

Item Type:Thesis (Master's thesis)
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Restricted to Caltech community only
Research Advisor(s):
  • Marcus, Rudolph A.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1983
Record Number:CaltechTHESIS:03292010-084636927
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:03292010-084636927
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5640
Collection:CaltechTHESIS
Deposited By: Tony Diaz
Deposited On:15 Apr 2010 20:43
Last Modified:26 Dec 2012 03:23

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