The role of near-resonant intermediate states in the two-photon excitation of NO2: Origin bands in bent-to-linear transitions

Rochelle S. Tapper, Robert L. Whetten, Gregory S. Ezra, Edward R. Grant

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

The two-photon absorption spectrum of NO2 in the energy region from 55 000 to 60 000 cm-1 shows two new highly resolved band systems. The lower of these is recognized as the 3pσ 2Σu+ Rydberg state, higher members of which have been observed in previous work by conventional vacuum-UV absorption spectroscopy. The higher system is assigned to its companion 3pπ 2IIu Rydberg state, seen here for the first time. Both band systems evidence clear origins in bent-to-linear transitions, assignments which are confirmed by the rotational structure of individual bands. An important feature of these spectra is the high intensity of the origin and low-frequency cold bands, which deviates strongly from Franck-Condon predictions. We suggest that this behavior can be explained by intramolecular relaxation within the continuum of intermediate states resonant with the first photon.

Original languageEnglish (US)
Pages (from-to)1273-1275
Number of pages3
JournalJournal of physical chemistry
Volume88
Issue number7
DOIs
StatePublished - 1984
Externally publishedYes

ASJC Scopus subject areas

  • General Engineering
  • Physical and Theoretical Chemistry

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