Optical and bowl-to-bowl inversion properties of sumanene substituted on its benzylic positions; a DFT/TD-DFT study

Armaković, Stevan; Šetrajčić, Jovan P.; Šetrajčić, Igor J.

doi:10.1016/j.cplett.2013.05.061

Cited by 48 publications

(26 citation statements)

References 33 publications

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“…The introduction of BH/ NH groups increased/decreased bond lengths between atom at benzylic position and near carbon atoms. These structural changes are related to the changes of bowl depth [10] which is dictated by the size of substituent, as stated by Priyakumar et al [11]. Larger substituent tends to flatten the structure and vice versa.…”

Section: Resultsmentioning

confidence: 90%

“…Consequently, the increased recombination of electrons and holes in this derivate might lead to the decrease of optical properties related with exciton subsystem. In our previous work [10] it is shown that of all investigated derivatives precisely this derivate has the lowest absorption properties in the UV spectra. Exciton binding energies of 0.8 nm carbon nanotubes are found to be around 0.4 eV, as reported in [63] while the exciton binding energies of conventional bulk semiconductors such as GaAs have values of around 0.01 eV, due to strong Coulombic interactions [64].…”

Section: Exciton Binding Energiesmentioning

confidence: 97%

“…UV/Vis information were taken from our previous work [10] where simulations were done at the same level of theory with 6-31++G(d,p) basis set.…”

Section: Computational Detailsmentioning

confidence: 99%

“…For instance, thanks to the significant charge separation, the sumanene dipole moment is relatively high and can induce a dipole moment in the molecules such as hydrogen, thus allowing the process of physisorption to happen [9]. The potential of sumanene is also seen in its structural features; it has three benzylic carbon atoms suitable for effective functionalization [10]. Another important structural feature is its bowl depth, which is significantly higher than in its "elder brother"-corannulene.…”

Section: Introductionmentioning

confidence: 98%

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Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

2014

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We investigated the effects of substitution on the sumanene benzylic CH2 groups with BH and NH groups using density functional theory computations. Our study shows that various properties of sumanene could be finely tuned for the application in the areas closely related to the materials science. Structural properties are significantly altered with such modifications and other properties as well. Charge distributions were evaluated through natural population analysis (NPA), while stability of investigated structures was investigated using quantum molecular descriptors. Using molecular orbital analysis further insight into the effects of substitution was obtained. Potential of sumanene as a candidate for application in the field of organic electronics is assessed through calculations of exciton binding energy. Non-linear optical properties of investigated structures were investigated using the first hyperpolarizability tensor. Special attention was paid to the aromaticity of sumanene. This property was evaluated employing NICS parameter while for detailed study of obtained results we used NBO and NBOdel analysis.

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Section: Resultsmentioning

confidence: 90%

Section: Exciton Binding Energiesmentioning

confidence: 97%

“…UV/Vis information were taken from our previous work [10] where simulations were done at the same level of theory with 6-31++G(d,p) basis set.…”

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

2014

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“…18 The majority of papers on this topic have been published in the 1990s; [19][20][21] however, also in very recent times, joint experimental-computational studies have been conducted. 22,23 More recently, the experimental and computational interest in inversion barriers has moved to bowl-shaped molecules, such as corannulene, [24][25][26][27][28][29] sumanene and its derivatives, [29][30][31][32] and other bowl-shaped hydrocarbons, including some derived from fullerene fragments. [33][34][35][36] Also, bowl-shaped and warped ("pringleshaped") boron nitride (BN) and aluminum nitride analogues of those hydrocarbons have been studied.…”

Section: Introductionmentioning

confidence: 99%

The INV24 test set: how well do quantum-chemical methods describe inversion and racemization barriers?

Goerigk

Sharma

2016

Can. J. Chem.

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For years, there has been ongoing interest in experimentally and theoretically understanding inversion and racemization processes. However, to the best of our knowledge, there has been no computational study that systematically investigated how well low-level quantum-chemical methods predict inversion barriers. Herein, we provide an answer to this question and we present the INV24 benchmark set of 24 high-level, ab initio inversion barriers. INV24 covers inversion in triatomics, in pyramidal molecules, in one cyclic system, and in various helical and bowl-shaped compounds. Our results indicate that previously applied DFT approximations combined with small basis sets are not reliable enough and that at least a triple-basis is needed for meaningful results. Moreover, we show that intramolecular London dispersion influences the barriers by 2 kcal/mol or more and that dispersion corrections should always be applied to DFT results. With our analysis of 34 DFT approximations, we can reproduce the well-known Jacob's Ladder scheme with (meta-)generalized-gradient-approximation methods underestimating barriers and global-hybrid DFT functionals performing better. Range-separated hybrids or Minnesota-type hybrids are not particularly superior to more conventional methods, such as B3LYP-D3. The by far best results are achieved with dispersioncorrected double hybrids, which give results below the chemical accuracy target of 1 kcal/mol. They also outperform wavefunction second-order perturbation theory approaches and we recommend using them whenever possible. Given that our systematic study of INV24 is the first of its kind, our findings have the potential to change common practice in this field and they will guide future investigations of inversion processes.Key words: barrier heights, chemical inversion, racemization barriers, benchmarking, density functional theory, wave-function theory.Résumé : Depuis des années, il y a un intérêt pour comprendre de manière expérimentale et théorique les processus d'inversion et de racémisation. Cependant, à notre connaissance, aucune étude computationnelle n'a évalué de manière systématique la précision des méthodes de chimie quantique de bas niveau pour prédire les barrières d'inversion. Dans le cadre des présents travaux, nous offrons une réponse à cette question et présentons la base de référence INV24 de 24 barrières d'inversion ab initio de haut niveau. L'application de la base INV24 couvre l'inversion des systèmes triatomiques dans les molécules pyramidales, dans un système cyclique et dans divers composés hélicoïdaux et de forme concave. Nos résultats indiquent que les approximations de DFT appliquées antérieurement, combinées avec des bases de petite taille, ne sont pas assez fiables et qu'une base tripleest minimalement requise pour que les résultats soient significatifs. De plus, nous montrons que la dispersion intramoléculaire de London a une incidence de 2 kcal/mol ou plus sur les barrières et que les résultats de DFT doivent toujours être corrigés pour tenir compte...

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An effective tridental molecular clip for fullerenes

Denis

Krämer

Lee

et al. 2017

J of Physical Organic Chem

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By means of density functional calculations, we studied the performance of 2 fullerene receptors that contain 3 corannulene or triphenylene pincers. For the first time, we found a receptor that has a small tendency to form intramolecular stacks between the 3 corannulene pincers. After comparing their ability to trap fullerenes, with that of buckycatcher, buckycatcher-II, and the Venus flytrap, we conclude that a recordbreaking association constant is expected for the receptor with 3 corannulene pincers. Although triphenylene is less effective than the corannulene units in forming inclusion complexes with C 60 , the triphenylene-based host is also expected to have a high association constant. Finally, we discuss the theoretical problems found in reproducing the experimental free energy changes in solution for buckycatcher, buckycatcher-II, and the Venus flytrap.

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Optical and bowl-to-bowl inversion properties of sumanene substituted on its benzylic positions; a DFT/TD-DFT study

Cited by 48 publications

References 33 publications

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

The INV24 test set: how well do quantum-chemical methods describe inversion and racemization barriers?

An effective tridental molecular clip for fullerenes

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