Development of a TDDFT-Based Protocol with Local Hybrid Functionals for the Screening of Potential Singlet Fission Chromophores

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00480952" target="_blank" >RIV/61388963:_____/17:00480952 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1021/acs.jctc.7b00699" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.7b00699</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.7b00699" target="_blank" >10.1021/acs.jctc.7b00699</a>

Result language

angličtina

Original language name

Development of a TDDFT-Based Protocol with Local Hybrid Functionals for the Screening of Potential Singlet Fission Chromophores

Original language description

Chromophores suitable for singlet fission need to meet specific requirements regarding the relative energies of their S-0 S-1, and T-1 (and T-2) electronic states. Accurate quantum chemical computations of the corresponding energy differences are thus highly desirable for materials design. Methods based on density functional theory (DFT) have the advantage of being applicable to larger, often more relevant systems compared to more sophisticated post-Hartree-Fock methods. However, most exchange correlation functionals do not provide the needed accuracy, in particular, due to an insufficient description of the T-1 state. Here we use a recent singlet fission chromophore test set (Wen, J., Havlas, Z., Michl, J. J. Am. Chem. Soc. 2015, 137, 165-172) to evaluate a wide range of DFT-based methods, with an emphasis on local hybrid functionals with a position-dependent exact-exchange admixture. New reference vertical CC2/CBS benchmark excitation energies for the test set have been generated, which exhibit somewhat more uniform accuracy than the previous CASPT2-based data. These CC2 reference data have been used to evaluate a wide range of functionals, comparing full linear-response TDDFT, the Tamm-Dancoff approximation (TDA), and Delta SCF calculations. Two simple two-parameter local hybrid functionals and the more empirical M06-2X global meta-GGA hybrid provide the overall best accuracy. Due to its lower empiricism and wide applicability, the Lh12ct-SsifPW92 local hybrid is suggested as the main ingredient of an efficient computational protocol for prediction of the relevant excitation energies in singlet fission chromophores. Full TDDFT for the S-1, S-2, and T-2 excitations is combined with Delta SCF for the T-1 excitations. Making use also of some error compensation with suitable DFT-optimized structures, even the most critical T-1 excitations can be brought close to the target accuracy of 0.20 eV, while the other excitation energies are obtained even more accurately.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Volume of the periodical

13

Issue of the periodical within the volume

10

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

4984-4996

UT code for WoS article

000412965700031

EID of the result in the Scopus database

2-s2.0-85031036298