Ultraviolet two-photon spectroscopy of benzene: A new gerade Rydberg series and evidence for the 1 1E2g valence state

Robert L. Whetten, Ke Jian Fu, Edward R. Grant

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53 Scopus citations


In the first application of continuously tunable ultraviolet two-photon absorption spectroscopy to a study of the higher excited states of a polyatomic molecule, we have obtained the two-photon absorption spectrum of jet-cooled benzene in the energy region from 55 000 to 75 000 cm-1. The strongest features of this spectrum, seen as two-photon resonance structure in three-photon ionization, are assigned to members of a new Rydberg series. Vibronic elements of these Rydberg states show evidence of dynamical effects associated with a Jahn-Teller instability in the 2E1g ionic core toward which the series converges. Notably, the magnitude of vibronic coupling terms in these states appears quite comparable to that present in C6H6+ and the sym-halobenzene cation ground states, while differing significantly from theoretical calculations predicting v8 (ring stretch) as the major distorting mode. In addition, we observe two other new band systems: The first, with an origin at 60 800 cm -1, has vibronic structure, isotope shifts, and dramatically increased diffuseness upon deuteration, which taken together suggest its assignment as a highly valenized 3d Rydberg state or a degenerate valence state, most likely the lower of the two 1E2g states predicted by molecular orbital theory. The second, lying in the 55 000-58 000 cm -1 region, can be at least partially assigned to the two-photon forbidden 3px,y Rydberg states.

Original languageEnglish (US)
Pages (from-to)2626-2640
Number of pages15
JournalThe Journal of Chemical Physics
Issue number6
StatePublished - 1983
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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