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• W2009875790 abstract "A detailed examination of the phosphorescence excitation spectra of three aromatic ketones, acetophenone, p-bromoacetophenone and 1-indanone, has been carried out at both 77 and 4°K. The studies of 1-indanone demonstrate the following: (1) The 0–0 band of the S0 → S(n, π*) transition is allowed and polarized perpendicular to the plane of the molecule, indicating substantial delocalization of the oxygen long-pair orbital into the aromatic ring system. (2) Most of the intensity (80%–90%) in the S0 → S(n, π*) transition is vibronically induced. (3) A strong carbonyl progression appears to be absent in the S0 → S(n, π*) absorption spectrum, and this is attributed to mixing of the carbonyl stretching mode with other vibrational modes in the excited state. (4) The S0 → T(n, π*) transition has allowed character as a result of spin–orbit interaction between the T(n, π*) state and the La1(π, π*) state. (5) The intensification of the S0 → 1Lb transition in indanone relative to acetophenone is attributed to mixing of the Lb1 state with the La1 state induced by orthosubstitution. The introduction of La1 character into the Lb1 state is also responsible for the intensification of the S0 → T(n, π*) transition in indanone relative to acetophenone. (6) The 0–0 band of the S0 → T(π, π*) transition is allowed by spin–orbit coupling with the allowed, out-of-plane polarized component of the S0 → S(π, π*) transition. (7) Vibronic coupling between the T(π, π*) state and a nearby T(n, π*) state introduces significant in-plane polarized intensity into the S0 → T(π, π*) transition. Essentially similar results were obtained with acetophenone and p-bromoacetophenone, with the exception that the strong S0 → T(π, π*) transition in p-bromoacetophenone was found to be in-plane polarized parallel to the long-axis polarized transition to the La1(π, π*) state. Diffuseness observed in the 4°K single-crystal S0 → T spectra of each of the three compounds is attributed to vibronic interaction of the T(n, π*) with nearly degenerate vibronic levels associated with a lower-lying T(π, π*) state." @default.
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• W2009875790 date "1970-03-01" @default.
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• W2009875790 title "Investigation of S → T and S → S Transitions by Phosphorescence Excitation Spectroscopy VII. 1-Indanone and Other Aromatic Ketones" @default.
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• W2009875790 doi "https://doi.org/10.1063/1.1673283" @default.
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