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Volumn 113, Issue 22, 2000, Pages 10002-10012

Excited state localization in organic molecules consisting of conjugated and nonconjugated segments

Author keywords

[No Author keywords available]

Indexed keywords

CARRIER CONCENTRATION; CORRELATION METHODS; ELECTRON SPECTROSCOPY; LUMINESCENCE; MATHEMATICAL OPERATORS; ORGANIC POLYMERS; RELAXATION PROCESSES; WAVE EQUATIONS;

EID: 0034516420     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1323263     Document Type: Article
Times cited : (60)

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    • The AMI calculations yield a total energy that is only 0.3 kcal/mol lower for the fully optimized molecule I than for a conformation with a planar core; see also O. Lhost and J. L. Brédas, J. Chem. Phys. 96, 5279 (1992).
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    • note
    • With a CI active space scaled according to the number of π orbitals in the molecule, the lowest-lying excited state in trans-stilbene is calculated to be 0.25 eV above the corresponding state in compound I.
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    • note
    • In fact, the order of the lowest three excited states is affected by the level of correlation included in the INDO/SCI calculations. In our approach, we have scaled the CI active space according to the number of π electrons in the system. Including excitations from the highest 34 occupied to the lowest 34 unoccupied molecular orbitals in compound I yields the two optically forbidden states 0.02 eV below the state dominated by the HOMO→LUMO transition (see Table I). However, calculations performed with a much smaller (larger) CI active space including the highest 10 (60) occupied and lowest 10 (60) unoccupied levels locate the forbidden states 0.04 (0.05) eV above the optically allowed excited state.
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    • Benjamin, New York, Chap. 7
    • The lowest-lying excited state in an isolated naphthalene molecule is calculated at the INDO/SCI level at 3.98 eV and is optically forbidden. See also, e.g., L. Salem, The Molecular Orbital Theory of Conjugated Systems (Benjamin, New York, 1966), Chap. 7.
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    • note
    • A very weak (reduced by a factor of about 30) emission occurs at higher energies when exciting the sample at 4.43 eV. However, we attribute this feature to contaminations of the investigated material rather than to emission from higher-lying states because its relative intensity changes between different samples.


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