Theoretical Study on Third-Order Nonlinear Optical Property of One-Dimensional Cyclic Thiazyl Radical Aggregates: Intermolecular Distance, Open-Shell Nature, and Spin State Dependences

Hiroshi Matsui, Masaki Yamane, Takayoshi Tonami, Masayoshi Nakano, Marc De Wergifosse, Tomasz Seidler, Benoît Champagne

Résultats de recherche: Contribution à un journal/une revueArticleRevue par des pairs

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 originaleAnglais
Pages (de - à)6779-6785
Nombre de pages7
journalJournal of Physical Chemistry C: Nanomaterials and interfaces
Volume122
Numéro de publication12
Les DOIs
Etat de la publicationPublié - 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 fondsNuméro du bailleur de fonds
Belgian Government
FNRS‐FRFC2.4.617.07
IUAP
Research Center for Advanced Materials Science at King Khalid University
Japan Society for the Promotion of ScienceJP26107004, JP17H05157, JP24109002, 25248007, 15J05489
King Khalid University RCAMS/KKU/001-16

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      CHAMPAGNE, B. (Responsable du Projet), Lazzaroni, R. (Responsable du Projet), Geuzaine , C. (Co-investigateur), Chatelain, P. (Co-investigateur) & Knaepen, B. (Co-investigateur)

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