Interstate coupling and dynamics of excited singlet states of isolated diphenylbutadiene |
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| Institution: | 1. School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin 30071, PR China;2. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 30071, PR China;1. Karabuk University, Engineering Faculty, Mechanical Engineering Department, Baliklar Kayasi Mevkii Demir Celik Kampusu, Karabuk, 78050, Turkey;2. University of Ontario Institute of Technology, Faculty of Engineering and Applied Science, Mechanical Engineering Department, 2000 Simcoe St N, Oshawa L1H 7K4, Ontario, Canada;3. Faculty of Mechanical Engineering, Yildiz Technical University, Istanbul, Turkey;3. Department of Human Biology, NUTRIM School of Nutrition and Translational Research in Metabolism, Maastricht University Medical Center, Maastricht, Netherlands;4. Research and Development, Human Nutrition and Health, DSM Nutritional Products Ltd., Basel, Switzerland;5. Nutrition, Metabolism, and Genomics Group, Division of Human Nutrition, Wageningen University, Wageningen, Netherlands |
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| 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, (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. |
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