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Abstract
Gas-phase E.P.R. spectra from the first six vibrational levels in X 3Σ- SO have been detected and analysed using a Hund's case (b) formalism. The spectra can be fitted using the following molecular constants:
The first and second derivatives of 
with respect to the normalized internuclear distance ξ were calculated from these constants. A simple analytic formalism is described which enables the variation of 
with internuclear distance to be separated into contributions from the matrix elements and from the change in energy spacing between interacting states. Both effects are important in the derivatives of 
, but it is suggested that in SO most of the variation of 
with rotational and vibrational state is due to the increase in the second-order part of the parameter as the separation between the ground and the dominant perturbing state decreases. This explanation implies that the expression proposed recently by Veseth and Lofthus for the rotational variation of 
is not accurate, and enables the conflict between the results of their analysis and ab initio calculations to be resolved.
A preliminary account of this work was read at the XIth International Symposium on Free Radicals held in Berchtesgaden/Königssee in September 1973.
A preliminary account of this work was read at the XIth International Symposium on Free Radicals held in Berchtesgaden/Königssee in September 1973.
Notes
A preliminary account of this work was read at the XIth International Symposium on Free Radicals held in Berchtesgaden/Königssee in September 1973.
