Describing excited states of [n]cycloparaphenylenes by hybrid and double-hybrid density functionals: from isolated to weakly interacting molecules

Sancho-García, Juan-Carlos; Adamo, Carlo; Pérez-Jiménez, Ángel J.

doi:10.1007/s00214-015-1778-4

Cited by 17 publications

(15 citation statements)

References 93 publications

(71 reference statements)

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“…It can be immediately seen how for the neutral N‐doped nanohoops 1 ‐ 3 a major absorbance peak is also observed around

340 - 350

nm, slightly red‐shifted on increasing the content of N in perfect agreement with experimental results . Note that contrarily to what was found before for the unsubstituted [8]CPP for these N‐doped [8]CPPs, the HOMO‐LUMO transition is not forbidden due to partial symmetry breaking induced by the presence of nitrogen, although the oscillator strength values are very low. Actually, for both [8]CPP and neutral N‐doped nanohoops 1 ‐ 3 , the transition (

π \to {normalπ}^{⋆}

) giving rise to the absorption maximum is composed of approximately equal combinations of one‐electron excitations from HOMO‐1 to LUMO and HOMO to LUMO + 1, and from HOMO‐2 to LUMO and HOMO to LUMO + 2.…”

Section: Resultssupporting

confidence: 87%

“…The M06‐2X and ωB97XD methods behave similarly, especially for the 1,15‐diaza‐[8]CPP 2 and N , N ‐dimethyl‐1,15‐diaza‐[8]CPP 2+ 8 cases, while B3LYP‐D3(BJ) lies between M06‐L and M06‐2X, following the increasing weight of the HF‐like exchange introduced into the method . We also note that the ωB97XD method had been shown previously to overestimate systematically the experimental absorption maxima for the set of increasingly longer [

6 - 12

]CPPs, and we will, thus, rely in the following in the B3LYP‐D3(BJ) optimized geometries as a compromise. We calculate with this method a diameter of

11.0 \pm 0.5

Å for molecule 1 , to be compared with an experimental (X‐ray) value of

10.9 \pm 0.2

Å, [31] and that the precise location of the N atom could not be experimentally resolved, which precludes a more detailed comparison between experimental and theoretical results for individual bond lengths.…”

Section: Resultsmentioning

confidence: 54%

See 1 more Smart Citation

N‐doped cycloparaphenylenes: Tuning electronic properties for applications in thermally activated delayed fluorescence

Graham

Moral²,

Muccioli

et al. 2017

Int J of Quantum Chemistry

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We theoretically characterize a series of substituted cycloparaphenylene nanohoops to study the effect of incorporating an electron-withdrawing group into their cyclic structure. We systematically vary the nature, position, and number of nitrogen-containing acceptor groups in both neutral (pyridine) and charged forms (pyridinium and methylpyridinium) to provide insights into how this functionalization affects the structural, electronic, and optical properties of these systems. We focus also on the singlet-triplet energy difference, with low values found, which might pave the way to further applications in the field of devices for light-emitting applications providing a potential class of TADF-based emitters. K E Y W O R D S density functional theory, donor-acceptor cycloparaphenylenes, optoelectronic properties, TD-DFT, thermally activated delayed fluorescence | I N TR ODU C TI ONOrganic Electronics is a field of rapid growth attracting interest from interdisciplinary domains including electronics & engineering, chemistry, physics, and materials science, not to mention the great commercial interest toward its applications. [1,2] The facile tunability of organic molecules has paved the way for a wealth of organic-based materials to be synthesized with novel key properties. Already, small organic molecules find their place in photovoltaic cells, [3,4] light-emitting transistors, [5][6][7][8][9] and diodes, [10][11][12] to name just a few of these applications. The flexibility of organic materials over inorganic has enabled the birth of the "soft electronics" market, including devices that can twist, bend or mould to any surface or textile. With so many possibilities arising from unique properties of organic molecules, the future of organics appears bright: not only do organic materials promise more innovative technologies but also are far more sustainable (organic molecules are abundant, easily synthesized and potentially Int J Quantum Chem. 2018;118:e25562.

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“…It can be immediately seen how for the neutral N‐doped nanohoops 1 ‐ 3 a major absorbance peak is also observed around

340 - 350

π \to {normalπ}^{⋆}

Section: Resultssupporting

confidence: 87%

6 - 12

]CPPs, and we will, thus, rely in the following in the B3LYP‐D3(BJ) optimized geometries as a compromise. We calculate with this method a diameter of

11.0 \pm 0.5

Å for molecule 1 , to be compared with an experimental (X‐ray) value of

10.9 \pm 0.2

Section: Resultsmentioning

confidence: 54%

N‐doped cycloparaphenylenes: Tuning electronic properties for applications in thermally activated delayed fluorescence

Graham

Moral²,

Muccioli

et al. 2017

Int J of Quantum Chemistry

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“…The idea of DH scheme can be traced back to the work of Ernzerhof which used by Zhao et al through the multi‐coefficient methods and finally popularized by Grimme, the author of the B2‐PLYP model. In recent years, a large number of DHs with variety of density functional approximations (DFAs) has been proposed and validated on different properties . We refer the interested reader to the recent review articles in the field of DH‐DFT …”

Section: Theoretical and Methodological Frameworkmentioning

confidence: 99%

Order of stabilities in water nanoclusters: Insight from some recent double‐hybrid functionals

Fallahzadeh

2016

Int J of Quantum Chemistry

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In the present work, the applicability of some of the recently proposed and modern double‐hybrid (DH) models and other density functional theory (DFT) approximations has been analyzed for a difficult test, the order of stability in low‐energy isomers of water nanoclusters. In particular, we aim to systematically investigate for these functionals the role played by several factors such as dispersion correction, integrand functions upon which the DHs are based, and different spin scaling for the perturbative term in DH calculations of the relative energies for various isomers of water nanoclusters (H2O)20. From the obtained results, the superior performance of DHs with respect to the functionals from previous rungs is confirmed. It is shown that the dispersion corrected DHs perform better than noncorrected counterparts. Plus, the DH models based on cubic integrand (CI) and quadratic integrand (QI) functions are nearly equivalent in performance. We also find that using only contributions of electron pairs with opposite spin for the perturbative correlation part through scaled opposite spin scheme does not represent a significant improvement on accuracy of the results. Putting all the results together, the dispersion corrected parameterized DHs and parameter‐free DH models involving CI and QI functions outperform other approximations for relative energies of water 20‐mers. Altogether, predicting the correct order of the stability in water nanoclusters may be considered as another Achilles' heel in DFT calculations, although more analyses in this context are still needed. © 2016 Wiley Periodicals, Inc.

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“…[ 281 ] This issue has also been investigated for selected 6CPP dimers representing the crystalline packing. [ 282 ] Depending on the relative orientation and distance between the monomers of these weakly interacting dimers, the excited‐state energies of isolated molecules (Ω) are splitted into

{normalΩ}^{'} = Ω \pm β

, with β the resonance energy given by the coupling between the ground‐state (CPP) and excited‐state (CPP ⋆ ) wavefunctions

⟨ {normalΨ}_{normalCPP} {normalΨ}_{{CPP}^{★}} | \hat{V} | {normalΨ}_{{CPP}^{★}} {normalΨ}_{normalCPP} ⟩

, with the results driven by long‐range interactions and differing for each excited state. Traditionally, single‐reference methods, such as TD‐DFT, can not describe the effects giving rise to this kind of excited‐states [ 283,284 ] and this has motivated the use of more advanced methods or corrections to standard TD‐DFT.…”

Section: Optical and Photophysical Propertiesmentioning

confidence: 99%

Theoretical Insights for Materials Properties of Cyclic Organic Nanorings

Pérez-Jiménez

Sancho-García

2020

Advcd Theory and Sims

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The synthesis of new carbon nanoforms with remarkable and fine-tuned bulk properties still represents a formidable challenge, with cyclic organic nanorings emerging in recent years for the template-driven design of this kind of systems. The design and engineering of these materials can be first controlled at the molecular scale, to further induce their specific self-assembly toward tailored properties at the nanoscale. Theoretical studies have lately contributed to the understanding of the underlying physical effects, the development of synthetic strategies, and the rationalization of novel materials properties, employing a variety of methods ranging from accurate calculations of isolated molecules to atomistic molecular dynamics simulations of a large sample of molecules in realistic conditions, which will be reviewed here with a focus on the transition from single-molecule to supramolecular properties.

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Describing excited states of [n]cycloparaphenylenes by hybrid and double-hybrid density functionals: from isolated to weakly interacting molecules

Cited by 17 publications

References 93 publications

N‐doped cycloparaphenylenes: Tuning electronic properties for applications in thermally activated delayed fluorescence

N‐doped cycloparaphenylenes: Tuning electronic properties for applications in thermally activated delayed fluorescence

Order of stabilities in water nanoclusters: Insight from some recent double‐hybrid functionals

Theoretical Insights for Materials Properties of Cyclic Organic Nanorings

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