INTENSITY CALCULATIONS FOR THE $\tilde{A}^{1} A_{u}(C_{2h}) - \tilde{X}^{1}\Sigma^{+}_{g}(D\infty_{h})$ TRANSITION OF ACETYLENE

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2001

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Ohio State University

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The $\tilde{A} - \tilde{X}$ transition of acetylene was the first electronic transition for which a change of point group was confirmed in $detail^{a}$. Previously, harmonic Franck-Condon calculations for this transition were $presented^{b}$. The present calculations allow for anharmonicity in the ground state, although the upper-state potential is still assumed to be $harmonic^{c}$. The transition moment is taken to be proportional to the $q^{\prime\prime}_{4}$ bending coordinate. For the calculation of the dispersed fluorescence $spectrum^{d}$ it is found that the global potential surface of Halonen, Child and $Carter^{e}$ gives the best qualitative agreement for the intensities, but could be improved for the energies of high bending states.

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$^{a}$C. K. Ingold and G. W. King, J. Chem. Soc., 2702-2755 (1953); K. K. Innes, J. Chem. Phys. 22, 863-876 (1954). $^{b}$J. K. G. Watson, Paper TG11, OSU Symposium (1998). $^{c}$J. D. Tobiason, A. L. Utz, E. L. Sibert III, and F. F. Crim, J. Chem. Phys. 99, 5762-5767 (1993). $^{d}$M. P. Jacobson, Ph.D. Thesis, Massachusetts Institute of Technology (1999); M. P. Jacobson and R. W. Field, J. Phys. Chem. 104, 3073 (2000). $^{e}$L. Halonen, M. S. Child, and S. Carter, Mol. Phys. 47, 1097 1982.
Author Institution: Centre for Experimental and Constructive Mathematics, Department of Mathematics, National Research Council of Canada

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