Assessment of the Density-Fitted Second-Order Quasidegenerate Perturbation Theory for Transition Energies: Accurate Computations of Singlet-Triplet Gaps for Charge-Transfer Compounds

Servan S. A., ÜNAL A., Hamarat B., BOZKAYA U.

JOURNAL OF PHYSICAL CHEMISTRY A, vol.124, no.34, pp.6889-6898, 2020 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 124 Issue: 34
  • Publication Date: 2020
  • Doi Number: 10.1021/acs.jpca.0c04555
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Aqualine, Aquatic Science & Fisheries Abstracts (ASFA), Artic & Antarctic Regions, Chemical Abstracts Core, Chimica, Compendex, Computer & Applied Sciences, EMBASE, INSPEC, MEDLINE
  • Page Numbers: pp.6889-6898
  • Hacettepe University Affiliated: Yes


Organic light-emitting diodes (OLEDs) have been of significant interest because of their superior performance and low cost of production. Thermally activated delayed fluorescence (TADF) has attracted significant interest in the OLED technology because it improves the efficiency of OLEDs by harvesting triplet excitons. Therefore, the accurate computation of singlet-triplet transition energies (Delta ES1-T1) of charge-transfer molecules is very important. However, the accurate computation of the Delta ES1-T1 values is a challenging problem for single-reference methods because of the multireference character of excited states. In this research, an assessment of density-fitted second-order quasidegenerate perturbation theory (DF-QDPT2) [Bozkaya, U.; J. Chem. Theory Comput. 2019, 15, 4415 - 4429] for singlet-triplet transition energies (Delta ES1-T1) of charge-transfer compounds is presented. The performance of the DF-QDPT2 method has been compared with those of several density-functional theory functionals, such as B3LYP, PBEO, M06-2X, omega B97X-D, and MN15; density-fitted state-averaged CASSCF (DF-SA-CASSCF); and single-state single- reference second-order perturbation theory (SS-SR-CASPT2) methods. For the TADF molecules considered, the DF-QDPT2 method provides a mean absolute error (MAE) of 0.13 eV, while the MAE values of DF-SA-CASSCF and SS-SR-CASPT2 are 0.65 and 0.74 eV, respectively. The performances of B3LYP and PBEO are slightly better than that of DF-QDPT2, while M06-2X and omega B97X-D provide noticeably higher errors compared with DF-QDPT2. Furthermore, the standard CASSCF without state-averaging yields dramatic errors with an MAE value of 3.0 eV. Our results demonstrate that eigenvalues of the DF-QDPT2-effective Hamiltonian can be reliably used for the prediction of singlet-triplet transition energies, while eigenvalues of DF-CASSCF/DF-SA-CASSCF fail to provide accurate predictions. Overall, we conclude that the DF-QDPT2 method emerges as a very useful tool for the computation of excited-state properties.