TY - JOUR
T1 - Interstate coupling and dynamics of excited singlet states of isolated diphenylbutadiene
AU - Amirav, Aviv
AU - Sonnenschein, Mark
AU - Jortner, Joshua
N1 - Funding Information:
We are grateful to Professor A.H. Zewail for stimulating correspondence and for pre-publication information. We are indebted to Professor J. Troe for his contribution to our understanding of intramolecular isomerization. This research was supported in part by the United States Army through its European Research Office (to JJ) and by the Basic Research Fund of the Israel Academy of Sciences and Humanities, Jerusalem (to AA).
PY - 1986/3/1
Y1 - 1986/3/1
N2 - 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, (τr/τr(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.
AB - 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, (τr/τr(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.
UR - http://www.scopus.com/inward/record.url?scp=0001417327&partnerID=8YFLogxK
U2 - 10.1016/0301-0104(86)80003-9
DO - 10.1016/0301-0104(86)80003-9
M3 - מאמר
AN - SCOPUS:0001417327
VL - 102
SP - 305
EP - 312
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 3
ER -