Interstate coupling and dynamics of excited singlet states of isolated diphenylbutadiene

Aviv Amirav*, Mark Sonnenschein, Joshua Jortner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

In this paper, we report on absolute fluorescence quantum yields from photoselected vibrational states of jet-cooled 1,4-diphenylbutadiene for excess vibrational energies, Ev = 0-7500 cm-1, above the apparent electronic origin of the S1(2Ag) state. The pure radiative lifetimes, τr, of the strongly scrambled S2(1Bu)-S1(2Ag) molecular eigenstates (Ev = 1050-1800 cm-1) show a marked dilution effect, (τrr(S2) ≈ 40), being practically identical with the τr values from the S1(2Ag) manifold (Ev = 0-900 cm-1), which is affected by near-resonant vibronic coupling to S2(1Bu) and exhibiting the dynamic manifestations of the intermediate level structure. Isomerization rates in the isolated molecule, which do not exhibit vibrational mode selectivity, were recorded over the energy range 0-6600 cm-1 above the threshold.

Original languageEnglish
Pages (from-to)305-312
Number of pages8
JournalChemical Physics
Volume102
Issue number3
DOIs
StatePublished - 1 Mar 1986

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