THE FRANCK-CONDON PRINCIPLE AND THE 3600$^{\circ}$ SYSTEM OF $CIO_{2}{^{*}}$

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1961

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Ohio State University

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A simple $method^{1}$ of applying the Franck Condon principle to polyatomic molecules leads to the geometrical structure of the excited electronic state of the 3600 {\AA} system of $ClO_{2}$. The calculation is based on the photographically measured relative intensities of the vibronic bands $v_{1}^{\prime}, v^{\prime}_{2}, 0)\leftarrow (0.0, 0)$ where $v_{1}^{\prime} = 0, 1, 2$ and $v^{\prime}_{2} = 0, 1$. Of the four excited state structures consistent with observed intensities the structure $(r^{\prime}^{\prime}; = 1.623$ {\AA}, $2_{\alpha}^{\prime} = 107^\circ 46^{\prime})$ agrees well with the structure known from the rotational spectra of the vibronic bands, $(r^{\prime} = 1.620 {\AA}, 2_{\alpha}^{\prime} = 107^\circ 24^{\prime})$. The structure of the ground, state used in this calculation is $(\Lambda^{\prime}^{\prime} = 1.472${\AA}, $2_{\alpha}^{\prime}^{\prime} = 117^{\circ} 24^{\prime})$. Certain excited state vibrational levels have been $previously^{2}$ interpreted as $1^{+}$ and $2^{+}$ of a double minimum potential in the anti-symmetrical coordinate $Q_{3}^{\prime}$. A double minimum potential $function^{3}$ consistent with the observed levels has been found. A Franck Condon calculation using the wave functions levels has been found. A Franck Condon calculation using the wave functions of these levels explains the relative intensities of some of the most prominent bands.

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$^{*}$Supported by the Air Force Office Of Scientific Research. $^{1}$J. B. Coon, R. E. DeWames, C. M. Loyd. To be published. $^{2}$J. B. Coon and E. Ortiz, J. Mol. Spectroscopy 1, 81 (1957). $^{3}$N.W. Naugle, J.R. Henderson and J. B. Coon, Bull. A. P. S. 4, 105 (1959).
Author Institution: A \& M College of Texas

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