First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions

R. R. Valiev, V. N. Cherepanov, G. V. Baryshnikov, D. Sundholm

Research output: Contribution to journalArticlepeer-review

35 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)6121-6133
Number of pages13
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number9
DOIs
Publication statusPublished - 2018

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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