Excited-State Behavior of trans and cis Isomers of Stilbene and Stiff Stilbene: A TD-DFT Study
The first part of the isomerization path on the two lowest excited states of trans and cis isomers of stilbene and stiff stilbene is investigated by means of TD-PBE0 calculations in the gas phase and in heptane solution. Solvent effects are taken into account by the PCM model. The excited-state opti...
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Published in | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 109; no. 44; pp. 10058 - 10067 |
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Main Authors | , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
10.11.2005
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Subjects | |
Online Access | Get full text |
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Summary: | The first part of the isomerization path on the two lowest excited states of trans and cis isomers of stilbene and stiff stilbene is investigated by means of TD-PBE0 calculations in the gas phase and in heptane solution. Solvent effects are taken into account by the PCM model. The excited-state optimized structures and the computed absorption and emission frequencies are in good agreement with the available experimental results. In all of the examined compounds, the isomerization process before barrier crossing occurs on the HOMO → LUMO bright state, whereas the role played by other single-excitation states appears negligible. The relative energy barriers on the isomerization paths are consistent with the experimental excited-state lifetimes, suggesting a unifying picture of the isomerization process in stilbene-like molecules. |
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Bibliography: | istex:AA4535B4B6648EFAC77636F471B898CA9E747656 ark:/67375/TPS-XCJ2QHDG-R ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp054250j |