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 |
|---|---|
| Pages (de - à) | 6779-6785 |
| Nombre de pages | 7 |
| journal | Journal of Physical Chemistry C |
| Volume | 122 |
| Numéro de publication | 12 |
| Les DOIs | |
| état | Publié - 29 mars 2018 |
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Theoretical Study on Third-Order Nonlinear Optical Property of One-Dimensional Cyclic Thiazyl Radical Aggregates : Intermolecular Distance, Open-Shell Nature, and Spin State Dependences. / Matsui, Hiroshi; Yamane, Masaki; Tonami, Takayoshi; Nakano, Masayoshi; De Wergifosse, Marc; Seidler, Tomasz; Champagne, Benoît.
Dans: Journal of Physical Chemistry C, Vol 122, Numéro 12, 29.03.2018, p. 6779-6785.Résultats de recherche: Contribution à un journal/une revue › Article
TY - JOUR
T1 - Theoretical Study on Third-Order Nonlinear Optical Property of One-Dimensional Cyclic Thiazyl Radical Aggregates
T2 - Intermolecular Distance, Open-Shell Nature, and Spin State Dependences
AU - Matsui, Hiroshi
AU - Yamane, Masaki
AU - Tonami, Takayoshi
AU - Nakano, Masayoshi
AU - De Wergifosse, Marc
AU - Seidler, Tomasz
AU - Champagne, Benoît
PY - 2018/3/29
Y1 - 2018/3/29
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85044765876&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.7b11319
DO - 10.1021/acs.jpcc.7b11319
M3 - Article
VL - 122
SP - 6779
EP - 6785
JO - Journal of physical chemistry. C
JF - Journal of physical chemistry. C
SN - 1932-7447
IS - 12
ER -