THE 2491 {\AA} BAND SYSTEM OF $NO_{2}$ ROTATIONAL STRUCTURE AND EVIDENCE FOR PRED ISSOCIATION IN THE ZERO-POINT LEVEL

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1976

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Ohio State University

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A detailed rotational analysis of the (0,0) band of the $2^{2}B_{2}- \tilde{X}^{2} A_{1}$ electronic transition of $NO_{2}$, at 2491 {\AA}, has been carried out. Although the lines are slightly broadened as a result of predissociation, it has been possible to determine the five quartic centrifugal distortion constants and the spin-rotation coupling constant $\epsilon_{aa}$ for the upper state. The centrifugal distortion constants allow the position of the unseen vibrational level $\nu_{3}^{\prime}$ to be estimated: the results offer no support to the suggestion of Coon, Cesani, and Huberman (J. Chem. Phys. 52, 1647 (1970)) that there is a double minimum potential function in the antisymmetric stretching coordinate of the $^{2}B_{2}$ state. The geometric structure of the zero-point level of the $^{2}B_{2}$ state is $r(N-O) = 1.3142$ {\AA}, ${\angle}ONO = 120.87^\circ$, and its lifetime (as calculated from the linewidths) is $42 \pm 5$ ps.

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Author Institution: Department of Chemistry, University of British Columbia

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