Theoretical Study of Singlet Fission in Oligorylenes

Minami, Takuya; Ito, Shinichiro; Nakano, Masayoshi

doi:10.1021/jz3011749

Cited by 89 publications

(123 citation statements)

References 42 publications

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“…The first triplet-tuned functional, TT-ωPBEh, was constructed by an internal matching of E T from two DFT variants, ∆SCF and TDDFT. To evaluate the behavior of TT-ωPBEh, we compared its errors for Similar to conventional optimally tuned functionals, [247][248][249][250][251][252][253][254][255][256] we expected a broad application of our triplet tuning approach for π-conjugated organic molecules that were considered theoretically challenging before. Beyond the accurate predictions of spectroscopy and dynamics, the method can set the stage for the computationally aided design and screening of photoactive materials.…”

Section: Discussionmentioning

confidence: 99%

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Lin

Voorhis

2019

J. Chem. Theory Comput.

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In the framework of density functional theory (DFT), the lowest triplet excited state, T 1 , can be evaluated using multiple formulations, the most straightforward of which are unrestricted DFT (UDFT) and time-dependent DFT (TDDFT). Assuming the exact exchangecorrelation (XC) functional is applied, UDFT and TDDFT provide identical energies for T 1 (E T ), which is also a constraint that we require our XC functionals to obey. However, this condition is not satisfied by most of the popular XC functionals, leading to inaccurate predictions of low-lying, spectroscopically and photochemically important excited states, such as T 1 and the lowest singlet excited state (S 1 ). Inspired by the optimal tuning strategy for frontier orbital energies [T. Stein, L. Kronik, and R. Baer, J. Am. Chem. Soc. 131, 2818 (2009)], we proposed a novel and non-empirical prescription of constructing an XC functional in which the agreement between UDFT and TDDFT in E T is strictly enforced. Referred to as "triplet tuning", our procedure allows us to formulate the XC functional on a case-by-case basis using the molecular structure as the exclusive input, without fitting to any experimental data. The first triplet tuned XC functional, TT-ωPBEh, is formulated as a long-range-corrected (LRC) hybrid of Perdew-Burke-Ernzerhof (PBE) and Hartree-Fock (HF) functionals [M. A. Rohrdanz, K. M. Martins, and J. M. Herbert, J. Chem. Phys. 130, 054112 (2009)] and tested on four sets of large organic molecules. Compared to existing functionals, TT-ωPBEh manages to provide 1 arXiv:1806.00317v3 [physics.chem-ph] 15 Jan 2019more accurate predictions for key spectroscopic and photochemical observables, including but not limited to E T , the optical band gap (E S ), the singlet-triplet gap (∆E ST ), and the vertical ionization potential (I ⊥ ), as it adjusts the effective electron-hole interactions to arrive at the correct excitation energies. This promising triplet tuning scheme can be applied to a broad range of systems that were notorious in DFT for being extremely challenging.

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Section: Discussionmentioning

confidence: 99%

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Lin

Voorhis

2019

J. Chem. Theory Comput.

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“…E S -2E T values for both perylene polymorphs are much smaller than in quaterrylene, consistent with the trend reported for single molecules based on TDDFT calculations. 56 Based on the energy conservation criterion, the best SF candidates are pentacene and monoclinic rubrene, 49 followed closely by quaterrylene. E S -2E T in quaterrylene is significantly higher than in tetracene and orthorhombic rubrene, where SF has been experimentally observed, therefore we conclude that SF is energetically favored with high efficiency in quaterrylene.…”

Section: Electronic and Optical Properties Of Perylene And Quaterrylenementioning

confidence: 99%

“…Oligorylenes [50][51][52][53][54][55] are another family of polycyclic aromatic hydrocarbons (PAHs) with unique thermodynamic, electronic, and excitonic properties, including SF. 56,57 The smallest member of this family, perylene, shown in Figure 1, has been reported to undergo SF from super-excited singlet states, as well as TTA. 58 Recently, SF has been measured experimentally in crystalline perylene derivatives.…”

Section: Introductionmentioning

confidence: 99%

On the possibility of singlet fission in crystalline quaterrylene

Wang

Liu

Cook

et al. 2018

The Journal of Chemical Physics

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Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E-2E) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

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“…68 Though the oligorylenes behave as connected naphthalenes (Figure 17a), it is predicted that the longer rylenes exhibit diradical character even in the neutral state. 69 Furthermore, early theoretical calculations have indicated the neutral polyrylene as either parallel polyacetylene chains (Figure 17b), or a planar poly( p-phenylene) bridged by double bonds (Figure 17c). 70,71 It is proved that the end groups or doping affect the whole electronic structure of the polyrylene.…”

mentioning

confidence: 99%

Studies on Pyrene and Perylene Derivatives upon Oxidation and Application to a Higher Analogue

Matsumoto

Suzuki

Hayashi

et al. 2017

Bulletin of the Chemical Society of Japan

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she was a researcher of PRESTO, JST, and then a group leader of CREST project (2010)(2011)(2012)(2013)(2014)(2015)(2016), JST, on "Construction of organic thin-film solar cells with innovative solutionprocessible organic materials". Her current research focuses on the development of functional organic materials including solution-processable molecular materials for organic electronics applications, large acenes and bottom-up synthesis of graphene nanoribbons. AbstractThe structure and electronic features of neutral and positively charged pyrene and perylene derivatives were explored. The radical cation of 1,3,6,8-tetraarylpyrene 1 was examined by ESR, UVvisNIR spectroscopy and theoretical calculations. The addition of 2 equiv of oxidant to 1 resulted in the formation of dication 1 2+. The single-crystal X-ray structure of 1 2+ proved that the aromatic part relocates from biphenyl unit to naphthyl unit upon 2e ¹ oxidation of 1. We have also investigated the oxidation processes of 3,9-diarylperylene 2 and 3,10-diarylperylene 3. The radical cations of 2•+ and 3 •+ showed ESR signals and the spin densities were proven to delocalize at 3,4,9,10-positions. In the case of doubly charged 3,9-diarylperylene, we could find the anthracene structure in the core, while the phenanthrene skeleton appeared in two-electron oxidized 3,10-diarylperylene. Finally we validated this phenomenon to apply for the higher analogue terrylene, discovering its large aromaticity relocation upon the 2e ¹ oxidation.

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Theoretical Study of Singlet Fission in Oligorylenes

Cited by 89 publications

References 42 publications

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

On the possibility of singlet fission in crystalline quaterrylene

Studies on Pyrene and Perylene Derivatives upon Oxidation and Application to a Higher Analogue

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