Role of Spin Polarization and Dynamic Correlation in Singlet–Triplet Gap Inversion of Heptazine Derivatives
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00576888" target="_blank" >RIV/61388955:_____/23:00576888 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11320/23:10475779
Result on the web
<a href="https://hdl.handle.net/11104/0346286" target="_blank" >https://hdl.handle.net/11104/0346286</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.3c00781" target="_blank" >10.1021/acs.jctc.3c00781</a>
Alternative languages
Result language
angličtina
Original language name
Role of Spin Polarization and Dynamic Correlation in Singlet–Triplet Gap Inversion of Heptazine Derivatives
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GF23-04302L" target="_blank" >GF23-04302L: Accurate and efficient density matrix renormalization group-based methods for extended molecules</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Theory and Computation
ISSN
1549-9618
e-ISSN
1549-9626
Volume of the periodical
19
Issue of the periodical within the volume
21
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
7606-7616
UT code for WoS article
001105081900001
EID of the result in the Scopus database
2-s2.0-85176140728