Excited state absorption spectroscopy and state ordering in polyenes. II. α,ω-diphenylpolyenes

Calculated and observed excited singlet state absorption (Sn←S1) spectra of a series of diphenylpolyenes are presented. In diphenyloctatetraene and diphenylhexatriene, the S1 state is assigned as an 1Ag state, in agreement with results from two-photon spectroscopic studies. In diphenylbutadiene, we...

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Veröffentlicht in:The Journal of chemical physics 1982-10, Vol.77 (7), p.3319-3328
Hauptverfasser: Goldbeck, Robert A., Twarowski, Allen J., Russell, Eric L., Rice, Jane K., Birge, Robert R., Switkes, Eugene, Kliger, David S.
Format: Artikel
Sprache:eng
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Zusammenfassung:Calculated and observed excited singlet state absorption (Sn←S1) spectra of a series of diphenylpolyenes are presented. In diphenyloctatetraene and diphenylhexatriene, the S1 state is assigned as an 1Ag state, in agreement with results from two-photon spectroscopic studies. In diphenylbutadiene, we assign the S1 state as a 1Bu, although two-photon studies have indicated that 1Ag state lies slightly below the 1Bu. It appears that a 1Ag state is the lowest excited state of diphenylbutadiene in its ground state geometry, but when the excited states relax to their equilibrium configurations, the 1Bu becomes the S1. Good agreement between the PPP–CI calculations and experimental Sn←S1 spectra demonstrates the potential usefulness of this technique in assigning ππ* excited states of large molecules.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.444250