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 (Sn) and triplet (Tn) wave functions. The electronic spin−orbit S1−Ti matrix elements, obtained from first-order perturbation theory, are used to compute the rates of intersystem crossing from the lowest singlet excited state, S1, into low-lying triplet states, Ti. 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.
Keywords
Intersystem crossingSinglet stateExcited stateSinglet fissionTriplet stateSpin–orbit interactionPhotochemistryMolecular physicsChemistryMaterials scienceChemical physicsPhysicsAtomic physicsCondensed matter physics
Affiliated Institutions
Related Publications
Spin–orbit coupling and inelastic transitions in collisions of O(1<i>D</i>) with Ar, Kr, and Xe
Inelastic collisions of O(1D) with Ar, Kr, and Xe have been treated in the multistate Landau–Zener and the close-coupling approximations. The coupling mechanism is spin–orbit mi...
REVERSIBLE, METASTABLE, ULTRAFAST PHOTOINDUCED ELECTRON TRANSFER FROM SEMICONDUCTING POLYMERS TO BUCKMINSTERFULLERENE AND IN THE CORRESPONDING DONOR/ACCEPTOR HETEROJUNCTIONS
The results of comprehensive studies of photoinduced electron transfer from semiconducting (conjugated) polymers to buckminsterfullerene are reviewed. Steady state and femtoseco...
The covalent and ionic states of the xenon halides
The electronic states and spectroscopic properties of the xenon halides, XeX (where X=F, C1, Br, I), are characterized on the basis of ab initio configuration interaction calcul...
Photoinduced Electron Transfer from a Conducting Polymer to Buckminsterfullerene
Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C 60 , is reported. After photo-excitation of the conjugate...
The electronic states of Ar+2, Kr+2, Xe+2. I. Potential curves with and without spin–orbit coupling
The low-lying states of Ar+2, Kr+2, and Xe+2 have been investigated using the POL CI method. Spin–orbit coupling has been included with a simple atoms-in-molecule approach. The ...
Publication Info
- Year
- 2001
- Type
- article
- Volume
- 105
- Issue
- 15
- Pages
- 3899-3907
- Citations
- 363
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
363
OpenAlex
2
Influential
346
CrossRef
Cite This
David Beljonne,
Zhigang Shuai,
Geoffrey Pourtois
et al.
(2001).
Spin−Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description.
The Journal of Physical Chemistry A
, 105
(15)
, 3899-3907.
https://doi.org/10.1021/jp010187w
Identifiers
- DOI
- 10.1021/jp010187w