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First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Valiev, Rashid R. Cherepanov, Victor N. Baryshnikov, Gleb V. Sundholm, Dage |
| Copyright Year | 2018 |
| Abstract | A method for calculating the rate constants for internal-conversion (kIC) and intersystem-crossing (kISC) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of kIC and kISC for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq3 and fac-Ir(ppy)3, which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq3 and fac-Ir(ppy)3 agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules. |
| Starting Page | 6121 |
| Ending Page | 6133 |
| Page Count | 13 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/c7cp08703a |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/c7/cp/c7cp08703a/c7cp08703a1.pdf |
| PubMed reference number | 29450414 |
| Alternate Webpage(s) | https://doi.org/10.1039/c7cp08703a |
| Journal | Medline |
| Volume Number | 20 |
| Issue Number | 9 |
| Journal | Physical chemistry chemical physics : PCCP |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
