Runnels, John Hulett (1983) Investigation of coriolis mixing in benzene. Master's thesis, California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:03292010-084636927
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)|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Restricted to Caltech community only|
|Defense Date:||1 January 1983|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||15 Apr 2010 20:43|
|Last Modified:||26 Dec 2012 03:23|
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