Electronic States of p -Benzoquinone. VI. Molecular Geometry in the Excited Electronic State of the 4500-A Absorption System as Derived from the Franck-Condon Principle

• Published in: The Journal of chemical physics 1960-06, Vol.32 (6), p.1611-1619
• Main Authors: Anno, Tosinobu, Sadô, Akira
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1730992

The method used for evaluating the Condon overlap integral associated with any vibronic band of an electronic absorption system of an XY2 molecule, as developed by J. B. Coon and his co-workers, is applied to more complex molecules. Thus, some information about the geometry of the excited electronic state of a complex molecule may be determined if the geometry in the ground state, the intensities of vibronic bands of the associated electronic absorption system, and normal coordinates and frequencies in both electronic states are known. The method is applied to the 4500-A absorption system of p-benzoquinone. Since the normal coordinate treatment for this molecule is only qualitatively valid, especially in its excited state, the results are expected to be more or less qualitative. If we take the resulting change of bond angles into account, the ring-bending frequency of species Au in the excited electronic state is calculated to be 438 cm—1 by the method described in Part III of this series [T. Anno and A. Sadô, Bull. Chem. Soc. Japan 31, 728 (1958)].