Projets par an
Résumé
Using the spin-unrestricted density functional theory method, we investigate the relationship between structure, spin state, and second hyperpolarizability (γ) of the finite and infinite one-dimensional open-shell aggregates composed of cyclic thiazyl radicals, that is, 1,2,3,5-dithiadiazolyl (DTDA) radicals. The DTDA aggregates with antiferromagnetic spin-alignment exhibit much greater enhancement of γ than the aggregates with ferromagnetic spin-alignment and the closed-shell benzene aggregates due to the intermediate open-shell singlet nature of the antiferromagnetic DTDA aggregate. It is found that this enhancement shows strong intermolecular distance dependences: the intermolecular distance giving the largest enhancement of γ decreases with increasing the number of molecules, and intermolecular distance alternation reduces the γ. For the infinite antiferromagnetic DTDA aggregate with a realistic intermolecular distance d = 3.1 Å, the γ per monomer reaches 1.9 × 106 au, which is comparable to that of the infinite open-shell singlet aggregate of phenalenyl radicals, and exhibits ∼2400 times enhancement as compared to that of the closed-shell benzene aggregate. This feature indicates the high-potential application of open-shell singlet cyclic thiazyl radical aggregates to outstanding third-order NLO materials.
langue originale | Anglais |
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Pages (de - à) | 6779-6785 |
Nombre de pages | 7 |
journal | Journal of Physical Chemistry C: Nanomaterials and interfaces |
Volume | 122 |
Numéro de publication | 12 |
Les DOIs | |
Etat de la publication | Publié - 29 mars 2018 |
Financement
This work was supported by funds from the bilateral agreement between the JSPS and the F.R.S-FNRS. This work is supported by JSPS KAKENHI Grant JP25248007 in Scientific Research (A), Grant JP24109002 in Scientific Research on Innovative Areas “Stimuli-Responsive Chemical Species”, Grant JP17H05157 in Scientific Research on Innovative Areas “π-System Figuration”, Grant JP26107004 in Scientific Research on Innovative Areas “Photosynergetics”, and Grant JP15J05489 in JSPS Research Fellowship for Young Scientists. This is also partly supported by King Khalid University through Grant RCAMS/KKU/001-16 under the Research Center for Advanced Materials Science at King Khalid University, Kingdom of Saudi Arabia. Theoretical calculations are partly performed using Research Center for Computational Science, Okazaki, Japan. The authors also acknowledge financial support from the Belgian Government (IUAP No. P7/5) and the Francqui Foundation. Part of the calculations were performed on the computers of the Consortium des Équipements de Calcul Intensif (CÉCI) and mostly those of the Technological Platform of High-Performance Computing, for which we gratefully acknowledge the financial support of the FNRS-FRFC (Conventions No. 2.4.617.07.F and 2.5020.11) and of the University of Namur.
Bailleurs de fonds | Numéro du bailleur de fonds |
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Belgian Government | |
FNRS‐FRFC | 2.4.617.07 |
IUAP | |
Research Center for Advanced Materials Science at King Khalid University | |
Japan Society for the Promotion of Science | JP26107004, JP17H05157, JP24109002, 25248007, 15J05489 |
King Khalid University | RCAMS/KKU/001-16 |
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CÉCI – Consortium des Équipements de Calcul Intensif
CHAMPAGNE, B. (Responsable du Projet), Lazzaroni, R. (Responsable du Projet), Geuzaine , C. (Co-investigateur), Chatelain, P. (Co-investigateur) & Knaepen, B. (Co-investigateur)
1/01/18 → 31/12/22
Projet: Recherche
Équipement
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Plateforme Technologique Calcul Intensif
Champagne, B. (!!Manager)
Plateforme technologique Calcul intensifEquipement/installations: Plateforme technolgique