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The electron-hole two-particle wave function for the singlet state, as defined in Ref. 20, is symmetric with respect to the electron and hole coordinates. This symmetry is found also in Ref. 22.
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In this context it is interesting to mention that the experimental emission spectrum of poly(fluorenone) peaks at 2.12 eV. [F. Uckert, Y.-H. Tak, K. Müllen, and H. Bässler, Adv. Mater. 12, 905 (2000)].
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Biphenyl (as an example for oliophenylenes) displays an inter-ring twist angle of 42° in the gas phase [A. Almenningen, O. Bastiansen, L. Fernholt, B. Cyvin, S. Cyvin, and S. Samdal, J. Mol. Struct. 128, 59 (1985)]
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0011271451
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4 are strongly underestimated both in TD-DFT and even more significantly in INDO/SCI.
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4FLO is unfortunately beyond present computational capacities.
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44
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0011308681
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note
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1 geometry.
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Recent studies have shown that at least in highly emissive materials the INDO/SCI calculated transition dipoles are in excellent agreement with experimental data of excited state lifetimes: E. Zojer, U. Rant, G. Leising, N. Schulte, A. Schlüter, P. Buchacher, R. Müllner, F. Stelzer, F. Wudl, and J.-L. Brédas, Mater. Res. Soc. Symp. Proc. 598, BB3.72.1 (2000)
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52
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0011364467
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note
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Due to the complications with the AM1/MECI approach outlined in the methodology section and in Ref. 31, performing this study ofr excited-state conformations would yield results which depended on the CI-active space chosen for the geometry optimizations. The active space might have to be adapted to the inter-ring twist angle and, therefore, the reliability of the obtained trends would not be satisfactory.
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An, C.9
Vardeny, Z.V.10
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