THE ELECTRONIC ABSORPTION SPECTRUM OF CARBON SUBOXIDE.
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Date
1969
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Ohio State University
Abstract
The gas phase absorption spectrum of the $1780{\AA}$ band of carbon suboxide has been measured photelectrically at both $300^{\circ}K$ and $200^{\circ}K$ with a 1-m monochromator having a $1.0{\AA}$ band width. The intensity of the 14 vibrational bands in the $1780{\AA}$ transition relative to each other remains unchanged on cooling to $200^{\circ}K$. This rules out the possibility that these bands are a vibrational sequence in the very low frequency $(63 cm^{-1})$ ground state bending mode and makes their assignment as a progression in a $400 cm^{-1}$ excited state bending vibration fairly definite. The regularity of this progression as it passes over the peak of the $1780{\AA}$ band implies that the linear-linear vertical transition is forbidden. Using the Herzberg-Teller theory of vibrational induced electronic transitions and a semi-empirical self-consistent field molecular orbital treatment of excited electronic states, strengths of both the $2650{\AA}$ and $1780{\AA}$ transitions have been calculated. The $2650{\AA}$ band ($^{1}\Sigma_{u}, \ ^{1}\Delta_{u} \leftarrow^{1}\Sigma^{+}_{g}$) combines with a $\pi_{g}$ vibration $(577 cm^{-1})$ to borrow intensity from the symmetry allowed $^{1}\Pi_{u} \leftarrow ^{1}\Sigma^{+}_{g}$ transition at $1587{\AA} (f \sim 1)$. The $1780{\AA}$ band ($^{1}\Sigma^{-}_{g} \ ^{1}\Sigma^{+}_{g}, \Delta_{g} \leftarrow \Sigma^{+}_{g}$) combines with the $\pi_{u}$ vibrations (63 and $660 cm^{-1}$) to also borrow intensity from the $1587{\AA}$ band. The temperature dependence of the intensity of the $1780{\AA}$ band will be compared with that predicted by the Herzberg-Teller theory.
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Author Institution: Department of Chemistry, Northeastern University