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Spin−Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description
Abstract
Configuration−interaction calculations are performed to describe the singlet and triplet excited states of oligothiophene and oligo(phenylene ethynylene) conjugated chains. Intersystem crossing from the singlet to the triplet manifold is made possible by spin−orbit coupling, which leads to a mixing of the singlet (S n ) and triplet (T n ) wave functions. The electronic spin−orbit S 1 −T i matrix elements, obtained from first-order perturbation theory, are used to compute the rates of intersystem crossing from the lowest singlet excited state, S 1, into low-lying triplet states, T i . On the basis of these results, a general mechanism is proposed to describe the intersystem crossing process in conjugated oligomers and polymers. The roles of chain length, heavy-atom derivatization, and ring twists are evaluated.
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Cites
Electron transfer reactions in chemistry. Theory and experiment
Marcus, R. A. (1993) · Reviews of Modern Physics · doi:10.1103/revmodphys.65.599 · Cited by 3,667
The Triplet State and Molecular Electronic Processes in Organic Molecules
Lower, S. K., & El-Sayed, M. A. (1966) · Chemical Reviews · doi:10.1021/cr60240a004 · Cited by 1,146
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Clarke, T. M., & Durrant, J. R. (2010) · Chemical Reviews · doi:10.1021/cr900271s · Cited by 2,372
Triplet photosensitizers: from molecular design to applications
Zhao, J., Wu, W., Sun, J., & Guo, S. (2013) · Chemical Society Reviews · doi:10.1039/c3cs35531d · Cited by 1,579
Samanta, P. K., Kim, D., Coropceanu, V., & Brédas, J.-L. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b12124 · Cited by 1,025
Self-citationNeto, B. A. D., Lapis, A. A. M., da Silva Júnior, E. N., & Dupont, J. (2013) · European Journal of Organic Chemistry · doi:10.1002/ejoc.201201161 · Cited by 328
Metadata
- Authors
- Beljonne, D., Shuai, Z., Pourtois, G., & Bredas, J. L.
- Venue
- The Journal of Physical Chemistry A
- Publisher
- American Chemical Society (ACS)
- Published
- 2001-03-15
- Volume
- 105
- Issue
- 15
- Pages
- 3899-3907
- ISSN
- 1089-5639 (ISSN-L)
- 1520-5215
- OpenAlex
- W2090648609
- Cited by
- 371
- References
- 2
- FWCI
- 4.60
- Type
- journal article
- Language
- en
- Open access
- closed
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- Beljonne, D., Shuai, Z., Pourtois, G., & Bredas, J. L. (2001). Spin−Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description. The Journal of Physical Chemistry A. https://doi.org/10.1021/jp010187w
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