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SOME FEATURES OF THE VIBRONIC ABSORPTION SPECTRUM OF CHLORINE $DIOXIDE^{*}$

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Title: SOME FEATURES OF THE VIBRONIC ABSORPTION SPECTRUM OF CHLORINE $DIOXIDE^{*}$
Creators: Coon, J. B.; Loyd, C. M.
Issue Date: 1955
Abstract: A critical list of 143 bands of the 3000-5000A absorption system of $Cl^{35}O_{2}$ has been compiled. This list is based on published data supplemented by the present authors. A vibrational analysis yields accurate values for three fundamental frequencies and all six anharmonicity constants of the excited electronic state. In addition, accurate values are obtained for the frequencies of the two symmetrical modes of the ground state and the three anharmonicity constants associated with these frequencies. Most of the assigned bands are arranged in thirteen $v^{\prime}_{1}$ progressions. The four most intense progressions designated by a (v), b (v), c (v), and d (v) are given the following assignments: a (v), very strong, $(v00)^{\prime} \rightarrow (000)^{\prime\prime}$; b (v), strong, $(v10)^{\prime} \rightarrow (000)^{\prime\prime}$; c (v), strong, $(v02)^{\prime} \rightarrow (000)^{\prime\prime}$; and d (v), medium, $(v04)^{\prime} \rightarrow (000)^{\prime\prime}$. A weak progression designated by m is given the assignment $(v12)^{\prime} \rightarrow (000)^{\prime\prime}$. The band intervals of any one of these progressions plotted versus $v_{1}$ should give a straight line of slope $2x^{\prime}_{11}$. This is observed to be the case above $v^{\prime}_{1} = 4$ where the slope is close to -4.88 for all five progressions. However, below $v^{\prime}_{1} = 4$ the slope is about -6.5 for progressions a and b, while the slope for progressions c, d, and m is approximately -3 at low $v^{\prime}_{1}$. This means that excited state vibrational levels with $v^{\prime}_{1} = 4$ are perturbed.\\ The relative values of the peak extinction coefficients have been determined for the bands of the four principle progressions. The most intense band of each progression is respectively: a (12), b (11), c (8), d (3). Condon overlap integrals calculated to the harmonic approximation give maximum intensity in all four progressions at the same value of $v^{\prime}_{1}$ namely $v^{\prime}_{1} = 6$ and $7.^{1}$
URI: http://hdl.handle.net/1811/7358
Other Identifiers: 1955-D-5
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