Bibi, Amna and Muhammad, Shabbir and UrRehman, Shafiq and Bibi, Shamsa and Bashir, Shahid and Ayub, Khurshid and Adnan, Muhammad and Khalid, Muhammad (2021) Chemically modified quinoidal oligothiophenes for enhanced linear and third-order nonlinear optical properties. ACS Omega, 6 (38). pp. 24602-24613. ISSN 2470-1343, DOI https://doi.org/10.1021/acsomega.1c03218.
Full text not available from this repository.Abstract
In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (alpha(iso)) polarizability value of 603.1 X 10(-24) esu is shown by compound 7 which is similar to 12, similar to 16, similar to 9, similar to 11, similar to 10, and similar to 4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability <gamma > with an amplitude of 7607 x 10(-36) esu at the M06/6-311G** level of theory, which is similar to 521, similar to 505, similar to 38, similar to 884, similar to 185, and similar to 15 times more than that of compounds 1-6, respectively. The extensively larger <gamma > amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.
| Item Type: | Article |
|---|---|
| Funders: | Deanship of Scientific Research in King Khalid University of Saudi Arabia [Grant No: RGP.2/128/42] |
| Uncontrolled Keywords: | Nonlinear optical (NLO); Molecular electrostatic |
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Faculty of Science > Department of Physics |
| Depositing User: | Ms Zaharah Ramly |
| Date Deposited: | 18 Jul 2022 03:49 |
| Last Modified: | 18 Jul 2022 03:49 |
| URI: | http://eprints.um.edu.my/id/eprint/33891 |
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