Role of Spin Polarization and Dynamic Correlation in Singlet–Triplet Gap Inversion of Heptazine Derivatives

Drwal, Daria; Matousek, Mikulas; Golub, Pavlo; Tucholska, Aleksandra; Hapka, Michał; Brabec, Jiri; Veis, Libor; Pernal, Katarzyna

doi:10.1021/acs.jctc.3c00781

Title: Role of Spin Polarization and Dynamic Correlation in Singlet–Triplet Gap Inversion of Heptazine Derivatives

Journal Article · 21 October 2023 · Journal of Chemical Theory and Computation

DOI: https://doi.org/10.1021/acs.jctc.3c00781 · OSTI ID:2203168

Drwal, Daria ^[1]; Matousek, Mikulas ^[2]; Golub, Pavlo ^[3];

^[1];

^[4]; Brabec, Jiri ^[3];

^[3];

^[1]

Lodz University of Technology (Poland)
Czech Academy of Sciences (CAS), Prague (Czech Republic); Charles Univ., Prague (Czech Republic)
Czech Academy of Sciences (CAS), Prague (Czech Republic)
Univ. of Warsaw (Poland)

The new generation of proposed light-emitting molecules for organic light-emitting diodes (OLEDs) has raised considerable research interest due to its exceptional feature—a negative singlet–triplet (ST) gap violating Hund’s multiplicity rule in the excited S₁ and T₁ states. We investigate the role of spin polarization in the mechanism of ST gap inversion. Spin polarization is associated with doubly excited determinants of certain types, whose presence in the wave function expansion favors the energy of the singlet state more than that of the triplet. Using a perturbation theory-based model for spin polarization, we propose a simple descriptor for prescreening of candidate molecules with negative ST gaps and prove its usefulness for heptazine-type molecules. Numerical results show that the quantitative effect of spin polarization decreases linearly with the increasing highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) exchange integral. Comparison of single- and multireference coupled-cluster predictions of ST gaps shows that the former methods provide good accuracy by correctly balancing the effects of doubly excited determinants and dynamic correlation. We also show that accurate ST gaps may be obtained using a complete active space model supplemented with dynamic correlation from multireference adiabatic connection theory.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Center for Scalable Predictive Methods for Excitations and Correlated Phenomena (SPEC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2203168

Alternate ID(s):: OSTI ID: 2471672

Journal Information:: Journal of Chemical Theory and Computation, Vol. 19, Issue 21; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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