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First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions
Tomsk State Univ, 36 Lenin Ave, Tomsk, Russia.;Univ Helsinki, Dept Chem, AI Virtanens Plats 1,POB 55, FI-00014 Helsinki, Finland..
Tomsk State Univ, 36 Lenin Ave, Tomsk, Russia..
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. Tomsk State Univ, 36 Lenin Ave, Tomsk, Russia.ORCID iD: 0000-0002-0716-3385
Univ Helsinki, Dept Chem, AI Virtanens Plats 1,POB 55, FI-00014 Helsinki, Finland..
2018 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 20, no 9, p. 6121-6133Article in journal (Refereed) Published
Abstract [en]

A method for calculating the rate constants for internal-conversion (k(IC)) and intersystem-crossing (k(ISC)) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k(IC) and k(ISC) 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-Alq(3) 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-Alq(3) 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.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2018. Vol. 20, no 9, p. 6121-6133
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-226797DOI: 10.1039/c7cp08703aISI: 000429280100014PubMedID: 29450414Scopus ID: 2-s2.0-85042794587OAI: oai:DiVA.org:kth-226797DiVA, id: diva2:1204396
Note

QC 20180508

Available from: 2018-05-08 Created: 2018-05-08 Last updated: 2018-05-08Bibliographically approved

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Baryshnikov, Gleb V.

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