Jahn-Teller effects in the spectra of open-shelled molecules
Abstract
The interaction of the doubly degenerate electronic state with the doubly degenerate vibrational mode to produce a simple but non-trivial Jahn-Teller effect in both the ground state and excited state is shown to satisfactorily explain both the absorption and emission spectra of gaseous silver trimer. The group-theoretical calculations for the j$\sp\prime$ = 3/2 states in D$\sb{\rm 3h}$ (e.g. silver trimer) and D$\sb{\rm 6h}$ (e.g. benzene cation) are shown to be of importance in determining the sign of the quadratic distortion parameter, g, and the vibronic phase angle, $\phi$, is definitively related to the normal coordinates for the $\nu\sb6$ doubly degenerate ring bending mode. Establishment of the correlation between the static electronic symmetries in D$\sb{\rm 2h}$ and the vibronic symmetries in D$\sb{\rm 6h}$ makes it possible to choose the minimum-energy configuration of the ground-state benzene cation.
Degree
Ph.D.
Advisors
Grant, Purdue University.
Subject Area
Chemistry
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