Abstract

Using photoelectron and optical spectroscopy, the ionization potentials of a large number of organic molecules in their Rydberg excited states were determined. In the limit of large alkyl substituents surrounding a central chromophoric group, it was found that the ionization potential of 3s, 3p, and 3d MO's are independent of the central group in direct contrast to the situation in the ground state. This is interpreted as showing that in the excited states of the limiting molecules, the Rydberg orbitals are completely n = 3 orbitals on the alkyl groups rather than on the central atoms as in the corresponding hydrides.

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